WO2014132881A1 - Ink composition for inkjet printing - Google Patents

Ink composition for inkjet printing Download PDF

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Publication number
WO2014132881A1
WO2014132881A1 PCT/JP2014/054116 JP2014054116W WO2014132881A1 WO 2014132881 A1 WO2014132881 A1 WO 2014132881A1 JP 2014054116 W JP2014054116 W JP 2014054116W WO 2014132881 A1 WO2014132881 A1 WO 2014132881A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
meth
dipentaerythritol
alkylene oxide
ink composition
Prior art date
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PCT/JP2014/054116
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French (fr)
Japanese (ja)
Inventor
直宏 高村
Original Assignee
第一工業製薬株式会社
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Publication date
Application filed by 第一工業製薬株式会社 filed Critical 第一工業製薬株式会社
Priority to CN201480009097.0A priority Critical patent/CN104995267A/en
Priority to KR1020217001481A priority patent/KR20210008943A/en
Priority to KR1020157022637A priority patent/KR102384738B1/en
Publication of WO2014132881A1 publication Critical patent/WO2014132881A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/30Inkjet printing inks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41JTYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01Ink jet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • a reactive functional group is introduced at the terminal of an alkylene oxide adduct of a pentaerythritol polymer as a crosslinkable (polyfunctional) monomer that is a main curable component.
  • a crosslinkable (polyfunctional) monomer that is a main curable component.
  • the crosslinkable monomer having an acrylate group introduced at the terminal has a relatively high viscosity at 25 ° C. of 580 mPas.
  • the scratch resistance of the obtained cured product seems to be such that it is not damaged by the nail (claw) or is damaged (paragraphs 100 to 102). That is, it seems that an improvement is desired in terms of viscosity and strength and fastness of the cured product.
  • the ink composition for inkjet printing of the present invention is particularly curable by irradiation with active energy rays such as ultraviolet rays, electron beams, blue visible rays, and gamma rays.
  • active energy rays such as ultraviolet rays, electron beams, blue visible rays, and gamma rays.
  • a light source including light within a wavelength range of 150 to 450 nm can be used, and if necessary, a photopolymerization initiator is included.
  • the combined use of heat by infrared rays, far infrared rays, hot air, high frequency heating or the like is also possible.
  • the average added mole number (L ⁇ m) of alkylene oxide per mole of dipentaerythritol is more than 0 and 5 or less, preferably 1 or more and 3 or less.
  • the average number of added moles of alkylene oxide is smaller than this range, the effect of reducing the viscosity of the crosslinking monomer and the effect of improving the photosensitivity become insufficient.
  • the viscosity of the crosslinkable monomer is increased, and it is necessary to increase the amount of the monofunctional (diluted) monomer in order to improve dischargeability.
  • the crosslink density is lowered by the length of the alkylene oxide chain, the strength of the cured product is lowered.
  • the crosslinkable monomer can be produced by, for example, the following method, but the production route is not particularly limited, and any production method can be adopted.
  • the reaction can be carried out while distilling off the water produced from (meth) acrylic acid and alkylene oxide-modified dipentaerythritol in the presence of an acid catalyst.
  • Any acid can be used without particular limitation as long as it is an acid used in a normal esterification reaction.
  • inorganic acids such as sulfuric acid and hydrochloric acid
  • organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid
  • acid type ion exchange resins such as fluorinated boron and ether complexes, lanthanide trif
  • Lewis acids such as fluorinated boron and ether complexes
  • lanthanide trif examples thereof include water-soluble Lewis acids such as rate. These acids may be used alone or in combination of two or more kinds.
  • the lower limit of the amount of acid used relative to the alkylene oxide-modified dipentaerythritol as a substrate is at least 0.1 molar equivalent, preferably at least 0.5 molar equivalent.
  • the upper limit is not limited, but is usually 20 mol equivalent or less, preferably 10 mol equivalent or less. If the amount of the acid catalyst is too small, the reaction progresses slowly or stops, which is not preferable. On the other hand, if the amount is too large, problems such as product coloring or catalyst remaining may occur, and Michael adduct formation may occur. It tends to cause undesirable side reactions such as
  • the lower limit of the reaction time is usually 30 minutes or more, preferably 60 minutes or more, and the upper limit is not particularly limited, but is usually 20 hours or less, preferably 10 hours or less.
  • HCF # 2650, HCF # 2600, HCF # 2350, HCF # 2300, MCF # 1000, MCF # 980, MCF # 970, MCF # 960, MCF88, manufactured by Mitsubishi Chemical Corporation examples include LFFMA7, MA8, MA11, MA77, MA100, and Printex 95, Printex 85, Printex 75, Printex 55, and Printex 45 manufactured by Degussa Huls.
  • examples of the metal powder for imparting conductivity include fine aluminum powder.
  • the particle diameter (weight average particle diameter) of the pigment is preferably 0.01 ⁇ m to 2.0 ⁇ m, more preferably 0.01 ⁇ m to 1.0 ⁇ m.
  • the blending amount of the pigment or the like is 1 to 60% by weight, preferably 5 to 40% by weight in the ink composition for ink jet printing.
  • a pigment dispersant or pigment derivative it is preferable to blend a pigment dispersant or pigment derivative together.
  • the pigment dispersant include ionic or nonionic surfactants, anionic and cationic surfactants.
  • nonionic polymer compounds can be used. Among these, a polymer compound containing a cationic group or an anionic group is preferable from the viewpoint of dispersion stability.
  • crosslinkable monomers can be used together with the above crosslinkable monomers, and noncrosslinkable monomers can be used together with such crosslinkable monomers.
  • the ratio of the crosslinkable monomer in the energy ray polymerizable monomer can be 55 to 90% by weight, preferably 65 to 80% by weight.
  • any monomer can be used as long as it undergoes a polymerization reaction when irradiated with energy rays.
  • Non-crosslinkable (monofunctional) (meth) acrylates include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( (Meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-brom
  • polymerization initiator examples include radical polymerization or cationic polymerization energy beam polymerization initiators, such as aromatic ketones, aromatic onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, ketoxime ester compounds, Examples thereof include compounds having a borate compound, an azinium compound, a metallocene compound, and an active ester compound.
  • radical polymerization or cationic polymerization energy beam polymerization initiators such as aromatic ketones, aromatic onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, ketoxime ester compounds, Examples thereof include compounds having a borate compound, an azinium compound, a metallocene compound, and an active ester compound.
  • the ink composition for ink jet printing of the present invention contains 5 to 10% by weight of an adhesion-imparting agent (such as a silane coupling agent) or a sensitizer, or 1 to 5% by weight of a solvent, if necessary. be able to. Furthermore, inorganic fine particles, dispersants, antifoaming agents, leveling agents, thixotropy imparting agents, slip agents, flame retardants, antistatic agents, antioxidants, ultraviolet absorbers, and the like can be contained in accordance with the purpose of use. .
  • an adhesion-imparting agent such as a silane coupling agent
  • a sensitizer such as a silane coupling agent
  • a solvent if necessary. be able to.
  • inorganic fine particles, dispersants, antifoaming agents, leveling agents, thixotropy imparting agents, slip agents, flame retardants, antistatic agents, antioxidants, ultraviolet absorbers, and the like can be contained in accordance with the purpose of use. .
  • sensitizer examples include ketocoumarin, fluorene, thioxanthone, diethylthioxanthone, isopropylthioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene.
  • Alkyl ether acetates and propylene glycol alkyl ether acetates include aromatic hydrocarbons (toluene, xylene, mesitylene, limonene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and And ethers such as tetrahydrofuran and 1,8-cineol. These may be used alone or in combination of two or more.
  • LC-MS analysis ⁇ Conditions for liquid chromatograph mass spectrometry (hereinafter abbreviated as LC-MS analysis)> LC-MS analysis of Examples and Comparative Examples was performed under the following conditions.
  • ⁇ Measurement conditions for hydroxyl value (OH value)> Acetic acid and pyridine were mixed at a weight ratio of 1: 9 to obtain an acetylating reagent.
  • the sample was weighed into a flask, an acetylating reagent was added and heated at 80 ° C. for 2 hours. After the reaction, titration was performed with 1 mol / l aqueous potassium hydroxide solution using phenolphthalein as an indicator.
  • Example 1 (Dipentaerythritol 3EO adduct acrylate-containing composition) ⁇ Synthesis of Dipentaerythritol 3EO Adduct Acrylate>
  • 254 g (1.0 mol) of dipentaerythritol manufactured by Guangei Chemical Industry Co., Ltd., OH number 1324
  • 127 g of toluene, and 0.3 g of KOH were charged, and the temperature was raised to 90 ° C. and stirred.
  • a slurry-like liquid was obtained.
  • the mixture was heated to 130 ° C., and 176 g (4 mol) of ethylene oxide was gradually introduced into the autoclave to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and a by-produced ethylene glycol polymer were removed by reducing the pressure at 140 ° C. under 10 mmHg of mercury. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7. The obtained dipentaerythritol 3EO adduct had an OH value of 897.
  • Example 2 (Dipentaerythritol 4EO adduct acrylate-containing composition) ⁇ Synthesis of Dipentaerythritol 4EO Adduct Acrylate>
  • 254 g (1.0 mol) of dipentaerythritol manufactured by Guangei Chemical Industry Co., Ltd., OH number 1324
  • 127 g of toluene, and 0.3 g of KOH were charged, and the temperature was raised to 90 ° C. and stirred.
  • a slurry-like liquid was obtained.
  • the mixture was heated to 130 ° C., and 220 g (5 mol) of ethylene oxide was gradually introduced into the autoclave to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and a by-produced ethylene glycol polymer were removed by reducing the pressure at 140 ° C. under 10 mmHg of mercury. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7. The obtained dipentaerythritol 4EO adduct had an OH value of 765.
  • Example 3 (Dipentaerythritol 5EO adduct acrylate-containing composition) ⁇ Synthesis of Dipentaerythritol 5EO Adduct Acrylate>
  • 254 g (1.0 mol) of dipentaerythritol manufactured by Guangei Chemical Industry Co., Ltd., OH number 1324
  • 36 g of distilled water 36 g
  • 0.3 g of KOH were charged, and the temperature was raised to 90 ° C.
  • the mixture was stirred to obtain a slurry liquid.
  • the mixture was heated to 130 ° C., and 264 g (6 mol) of ethylene oxide was gradually introduced into the autoclave to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and a by-produced ethylene glycol polymer were removed by reducing the pressure at 140 ° C. under 10 mmHg of mercury. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7. The OH value of the obtained dipentaerythritol 5EO adduct was 706.
  • ethylene glycol-modified dipentaerythritol (OH number 706) 477 g (1 mol), 562 g (7.8 mol) of acrylic acid, 52 g of paratoluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass four-necked flask, and air The reaction was conducted while blowing. Water generated by the reaction was removed from the system as needed by azeotroping with toluene. The reaction temperature was 100 to 110 ° C., and the amount of reaction water removed out of the system at the end of the reaction was 113 g.
  • Example 1 (Dipentaerythritol / hexaacrylate-containing composition) The same procedure as in Example 1 was performed except that dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was used in place of the above dipentaerythritol 3EO adduct acrylate.
  • dipentaerythritol hexaacrylate KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
  • Example 3 (EO-modified trimethylolpropane triacrylate-containing composition) The same procedure as in Example 1 was performed except that ethylene oxide-modified trimethylolpropane triacrylate (SR454 manufactured by Sartomer) was used in place of the dipentaerythritol 3EO adduct.
  • ethylene oxide-modified trimethylolpropane triacrylate SR454 manufactured by Sartomer
  • Example 4 Caprolactone-modified dipentaerythritol acrylate-containing composition
  • caprolactone-modified dipentaerythritol acrylate (KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.) was used instead of the above-mentioned dipentaerythritol 3EO adduct acrylate.
  • step tablet 25 steps, manufactured by Riston
  • the number of steps to be tack-free was described.
  • a high number of steps indicates a high degree of shading. That is, it can be cured even at a low exposure amount, and it can be said that the ink composition has high photosensitivity and excellent productivity.
  • a cured film was prepared on an easy-adhesion-treated PET film (Lumilar T-60 manufactured by Toray Industries, Inc.) by the same method as the evaluation of the curability. And the state of the coating film at the time of grind
  • a cured film was prepared on a PET film (Lumilar T-60 manufactured by Toray Industries, Inc.) by the same method as the curable item, and a cured film was prepared by the same method as the curable item.
  • One point of the four corners of the film was fixed on a flat surface, and the heights of the remaining three points at that time were measured, and the average value was defined as curl.
  • Dischargeability was evaluated using a dischargeability evaluation apparatus (“inkjet drawing / coating apparatus”; NanoPrinter-300 manufactured by Microjet). This evaluation apparatus performs drawing for one head scan by a plurality of nozzles of a piezoelectric element method.
  • the atmospheric temperature in the measurement chamber was 25 ° C. ; No nozzle clogging: ⁇ , Nozzle clogging: ⁇ .
  • the ink compositions of Examples 1 to 3 of the present invention have improved ejection properties compared to Comparative Example 1 using dipentaerythritol hexaacrylate. I was able to. This was considered to be because the viscosity of the crosslinkable monomer itself could be reduced by moderate ethylene oxide modification.
  • the dischargeability was greatly improved as compared with a similar acrylate obtained by adding 12 moles of ethylene oxide to dipentaerythritol (dipentaerythritol 12EO adduct acrylate).
  • a considerable improvement was seen compared to a similar acrylate obtained by adding 8 mol of ethylene oxide to dipentaerythritol (dipentaerythritol 8EO adduct acrylate).
  • Comparative Examples 2 to 4 as a result of using a crosslinkable (polyfunctional) monomer having a low viscosity and excellent discharge property, the discharge property and curling property were good, but the curability and steel wool resistance were low. .
  • the ink composition of each Example of the present application is controlled to the minimum required amount of ethylene oxide addition moles, while maintaining the steel wool resistance, the ink on the printing medium It was found that the deformation of the printed matter due to the curing shrinkage of the composition can be suppressed. Further, the curability was greatly improved as compared with Comparative Example 1 using dipentaerythritol hexaacrylate.
  • the reason why the curability is improved is considered that the mobility and the degree of freedom of the terminal acryloyl group are improved by the ethylene oxide modification.
  • specific data is not shown, the curability and steel wool resistance are greatly improved compared to the same acrylate (dipentaerythritol 12EO adduct acrylate) obtained by adding 12 moles of ethylene oxide to dipentaerythritol. It was. In addition, a considerable improvement was seen compared to a similar acrylate obtained by adding 8 mol of ethylene oxide to dipentaerythritol (dipentaerythritol 8EO adduct acrylate).
  • the alkylene oxide-modified dipentaerythritol (meth) acrylate represented by the above general formulas (I) and (II) and having an optimized number of added moles of alkylene oxide (AO) is used as a crosslinkable monomer.
  • the ink composition for ink-jet printing exhibits low viscosity for good dischargeability, good photosensitivity and curability, and low shrinkage, and the cured product has good scratch resistance. Therefore, it can be suitably used as an ink composition for ink jet printing for printing or coating requiring water resistance and fastness.
  • electrical circuit products such as printed wiring boards. For example, formation of an insulating film at a predetermined position after wiring formation, formation of a resist pattern for vapor deposition / sputtering, etc. Can be used.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided is an ink composition for inkjet printing which maintains low values for the viscosity of a cross-linkable monomer and the shrinkage upon curing, and exhibits favorable curability and abrasion resistance of the cured product thereof. An alkylene oxide-modified dipentaerythritol (meth)acrylate having a structure represented by general formulas (I) and (II) is used as a cross-linkable monomer. (I) (II) The average polymerization degree (L) of the added alkylene oxide chain satisfies the relationship 0<L≤5; the average value of m is more than 0 and not more than 6; the average number of added moles (L×m) of the alkylene oxide satisfies the relationship 0<L×m≤5; n is 1 or 2; the average value of o is 0-5, inclusive; and the sum of m, n and o is 6. R2 represents a hydrogen atom or a methyl group.

Description

インクジェット印刷用インキ組成物Ink composition for inkjet printing
 本発明は、インクジェット方式での印刷または塗布に適した反応性のインキ組成物に関する。特には、紫外線(UV)、電子線(EB)等の活性エネルギー線の照射により即時に硬化可能なインキ組成物に関する。 The present invention relates to a reactive ink composition suitable for ink jet printing or coating. In particular, the present invention relates to an ink composition that can be instantly cured by irradiation with active energy rays such as ultraviolet rays (UV) and electron beams (EB).
 インクジェット方式での印刷または塗布は、紙への印刷のみならず、プラスチック材や繊維材などへの印字やパターン付与にも用いられており、近年は、電子・電気デバイスの製造のための配線形成、レジストパターン形成などにも用いられている。特に、活性エネルギー線により即時に硬化可能なインキ組成物を用いる場合、硬化後のインキが、耐水性、耐溶剤性、耐擦過性などを持つようにすることができるため、好ましい。 Inkjet printing or coating is used not only for printing on paper, but also for printing and patterning on plastics and fiber materials. In recent years, it has been used to form wiring for manufacturing electronic and electrical devices. It is also used for resist pattern formation. In particular, it is preferable to use an ink composition that can be instantly cured by active energy rays because the cured ink can have water resistance, solvent resistance, scratch resistance, and the like.
 特許文献1に記載のインクジェット印刷用インキ組成物においては、主たる硬化性成分をなす架橋性(多官能)モノマーとして、ペンタエリスリトール重合体のアルキレンオキシド付加物の末端に、反応性官能基を導入したものを用いている。しかし、具体的な実施例によると、末端にアクリレート基を導入した架橋性モノマー(実施例1)は、25℃での粘度が580mPasと、比較的高い。また、得られた硬化物の耐擦過性は、爪(つめ)で傷つかないか、または傷つくという程度であると思われる(100~102段落)。すなわち、粘度の点、及び、硬化物の強度や堅牢性の点で、改良が望まれるものと思われる。 In the ink composition for inkjet printing described in Patent Document 1, a reactive functional group is introduced at the terminal of an alkylene oxide adduct of a pentaerythritol polymer as a crosslinkable (polyfunctional) monomer that is a main curable component. Something is used. However, according to a specific example, the crosslinkable monomer having an acrylate group introduced at the terminal (Example 1) has a relatively high viscosity at 25 ° C. of 580 mPas. Further, the scratch resistance of the obtained cured product seems to be such that it is not damaged by the nail (claw) or is damaged (paragraphs 100 to 102). That is, it seems that an improvement is desired in terms of viscosity and strength and fastness of the cured product.
 特許文献2に記載のインクジェット印刷用インキ組成物は、特定の光重合開始剤と、表面調整剤としてのシリコーン系化合物を含有することなどを特徴としており、例えば実施例18及び実施例23では、架橋性(多官能)モノマーとして、ジペンタエリスリトール・ヘキサアクリレートをジアクリレート化合物とともに用いている(表3及び表4)。ところが、ヘキサアクリレートの含量が比較的少ない実施例18では、25℃での粘度が15mPasと低いものの、硬化性が「△」評価であり必ずしも充分でなかった(表8)。また、ヘキサアクリレートの含量が実施例18の2倍以上である実施例23では、硬化性が「○」評価であり良好であるものの、粘度が29mPasと、実施例18の約2倍となっている(表9)。すなわち、粘度及び硬化性をともに良好にするための、さらなる改良が望まれると思われる。 The ink composition for inkjet printing described in Patent Document 2 is characterized by containing a specific photopolymerization initiator and a silicone compound as a surface conditioner. For example, in Example 18 and Example 23, As a crosslinkable (polyfunctional) monomer, dipentaerythritol hexaacrylate is used together with a diacrylate compound (Tables 3 and 4). However, in Example 18 having a relatively low hexaacrylate content, although the viscosity at 25 ° C. was as low as 15 mPas, the curability was evaluated as “Δ” and not always sufficient (Table 8). Further, in Example 23 in which the content of hexaacrylate is more than twice that of Example 18, the curability is good with a ◯ evaluation, but the viscosity is 29 mPas, which is about twice that of Example 18. (Table 9). That is, it seems that further improvement for improving both viscosity and curability is desired.
 また、特許文献3に記載のインクジェット印刷用インキ組成物は、ε-カプロラクトンで変性されたジペンタエリスリトールヘキサアクリレートと、アリルグリコールとを含有することを特徴とするものである。架橋性モノマーをカプロラクトンで変性することで、硬化収縮を抑制しているが、カプロラクトンの鎖長が比較的大きいことから、架橋密度が低下し、硬化物の硬度、及び、耐擦過性が必ずしも充分でないと考えられる。 The ink composition for ink jet printing described in Patent Document 3 is characterized by containing dipentaerythritol hexaacrylate modified with ε-caprolactone and allyl glycol. Curing shrinkage is suppressed by modifying the crosslinkable monomer with caprolactone, but since the chain length of caprolactone is relatively large, the crosslinking density is reduced, and the hardness and scratch resistance of the cured product are not always sufficient. It is not considered.
 一方、特許文献4には、インクジェット方式により紫外線硬化性の樹脂を塗布することで、プリント基板を製造するためのレジストパターンを設けることが記載されている。 On the other hand, Patent Document 4 describes providing a resist pattern for manufacturing a printed circuit board by applying an ultraviolet curable resin by an inkjet method.
特開2011-132386JP2011-132386 特開2009-275175JP2009-275175 特開2010-202736JP2010-202736 特開2012-184411JP2012-184411
 本発明は上記に鑑みてなされたものであり、インクジェット印刷用インキ組成物において、架橋性モノマーの粘度及び硬化時の収縮性を低く保つとともに、硬化性、及び、硬化物の耐擦過性を良好とすることができるものを提供することにある。 The present invention has been made in view of the above, and in the ink composition for ink jet printing, the viscosity of the crosslinkable monomer and the shrinkage at the time of curing are kept low, and the curability and the scratch resistance of the cured product are good. It is to provide what can be.
 本発明者らは、上記課題を解決すべく鋭意検討を行った結果、架橋性モノマーとしてアルキレンオキサイド変性ジペンタエリスリトール(メタ)アクリレートを用いるとともに、この変性ジペンタエリスリトール(メタ)アクリレートとして、アルキレンンオキサイド付加モル数が、適度に少ないものを用いるならば、粘度及び硬化時の収縮性を低く保つとともに、硬化性、及び、硬化物の耐擦過性を良好なものとすることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors used alkylene oxide-modified dipentaerythritol (meth) acrylate as a crosslinkable monomer, and used this modified dipentaerythritol (meth) acrylate as an alkylene. It is found that if the number of moles of oxide added is moderately small, the viscosity and shrinkage at the time of curing can be kept low, and the curability and the scratch resistance of the cured product can be improved. The present invention has been completed.
 即ち、本発明のインクジェット印刷用インキ組成物は、下記一般式(I)及び(II)で表される構造を有したアルキレンオキサイド変性ジペンタエリスリトール(メタ)アクリレートを含有するものである。
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
 但し、一般式(I)中、Rは一般式(II)で表される置換基を表し、AOは-CH2CH2O-、-CH2CH(CH3)O-、-CH2CH2CH2CH2O-、又は-CH2CH(C25)O-で表されるアルキレンオキサイド単位の中から選択された1種又は2種以上を示し、付加しているアルキレンオキサイド鎖の平均重合度を示すLは0<L≦5であり、mの平均値は0より大きく5以下であり、アルキレンオキサイドの平均付加モル数L×mは0<L×m≦5であり、nは1もしくは2、oの平均値は0以上6以下であり、m、n及びoの合計値は6である。一般式(II)中、R2は水素原子又はメチル基を示す。
That is, the ink composition for inkjet printing of the present invention contains an alkylene oxide-modified dipentaerythritol (meth) acrylate having a structure represented by the following general formulas (I) and (II).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
In general formula (I), R represents a substituent represented by general formula (II), and AO represents —CH 2 CH 2 O—, —CH 2 CH (CH 3 ) O—, —CH 2 CH 1 or 2 or more types selected from alkylene oxide units represented by 2 CH 2 CH 2 O— or —CH 2 CH (C 2 H 5 ) O—, and an alkylene oxide chain added thereto L indicating the average degree of polymerization is 0 <L ≦ 5, the average value of m is greater than 0 and 5 or less, the average added mole number L × m of alkylene oxide is 0 <L × m ≦ 5, n is 1 or 2, the average value of o is 0 or more and 6 or less, and the total value of m, n, and o is 6. In the general formula (II), R 2 represents a hydrogen atom or a methyl group.
 本発明のインクジェット印刷用インキ組成物であると、主成分である架橋モノマーの度について、一般に用いられているジペンタエリスリトールアクリレートよりも大幅に低く、従来技術の誘導体よりも低くできる。そのため、特には無溶剤系の反応性組成物において、低粘度化・粘度調整のために添加される単官能モノマーの含有量を低減させ、又は添加しなくてもよくなる。また、このことから、反応性組成物中の重合性官能基である(メタ)アクリロイル基濃度を向上させることが可能となる。 In the ink composition for ink jet printing of the present invention, the degree of the crosslinking monomer as the main component is significantly lower than that of dipentaerythritol acrylate that is generally used, and can be lower than that of the prior art derivatives. Therefore, particularly in a solvent-free reactive composition, the content of the monofunctional monomer added for viscosity reduction and viscosity adjustment may be reduced or not added. This also makes it possible to improve the concentration of the (meth) acryloyl group that is a polymerizable functional group in the reactive composition.
 したがって、組成物の粘度が重要視されるインクジェット印刷用インキ組成物に配合する事で、ノズルからの吐出性を損なう事なく、インクの皮膜強度を維持する事が可能となる。さらには、架橋モノマーの光感度が、ジペンタエリスリトールアクリレートなどよりも高いので、生産性にも優れている。また、硬化時の収縮性を低く保つことができる。 Therefore, by blending with an ink composition for ink jet printing in which the viscosity of the composition is regarded as important, it is possible to maintain the film strength of the ink without impairing the discharge performance from the nozzle. Furthermore, since the photosensitivity of the crosslinking monomer is higher than that of dipentaerythritol acrylate or the like, the productivity is excellent. Moreover, the shrinkability at the time of hardening can be kept low.
 本発明のインクジェット印刷用インキ組成物は、上記一般式(I)、(II)で表される構造を有する架橋性モノマーを含有してなり、必要に応じて、この架橋性モノマーと反応する非架橋性モノマーを含む。また、必要に応じて、着色成分としての顔料または染料、または、導電性付与などのための金属微粉末などを含み、また、顔料を用いる場合、必要に応じて顔料分散剤を含む。 The ink composition for inkjet printing of the present invention contains a crosslinkable monomer having a structure represented by the above general formulas (I) and (II), and reacts with the crosslinkable monomer as necessary. Contains a crosslinkable monomer. Further, if necessary, it contains a pigment or dye as a coloring component, or a metal fine powder for imparting electrical conductivity, and when a pigment is used, it contains a pigment dispersant as necessary.
 本発明のインクジェット印刷用インキ組成物は、好ましくは、溶剤を全く含まない。また、溶剤を含む場合も、5重量%以下、好ましくは1重量%以下である。本発明のインクジェット印刷用インキ組成物は、好ましくは、25℃での粘度が、1~50mPasであり、より好ましくは3~15mPasである。この粘度の測定は、JIS K 5600-2-3に従って行うことができる。 The ink composition for inkjet printing of the present invention preferably contains no solvent. In the case of including a solvent, the content is 5% by weight or less, preferably 1% by weight or less. The ink composition for inkjet printing of the present invention preferably has a viscosity at 25 ° C. of 1 to 50 mPas, more preferably 3 to 15 mPas. This viscosity can be measured according to JIS K5600-2-3.
 本発明のインクジェット印刷用インキ組成物は、特には、紫外線、電子線、青色可視線、ガンマ線等の活性エネルギー線の照射により硬化可能なものである。紫外線を用いる場合、波長150~450nmの範囲内の光を含む光源を用いることができ、必要に応じて、光重合開始剤を含む。また、赤外線、遠赤外線、熱風、高周波加熱等による熱の併用も可能である。本発明のインクジェット印刷用インキ組成物の顔料以外の部分の中における、エネルギー線硬化性成分、特には紫外線硬化性成分の比率は、通常70~95重量%、典型的には80~90重量%である。なお、活性エネルギー線の照射による硬化は、例えば、吐出ノズルの直後に照射ランプを配置して、塗布とほぼ同時に行うこともでき、また、塗布パターンを完成した後に、照射装置内にセットして行うこともできる。 The ink composition for inkjet printing of the present invention is particularly curable by irradiation with active energy rays such as ultraviolet rays, electron beams, blue visible rays, and gamma rays. When ultraviolet rays are used, a light source including light within a wavelength range of 150 to 450 nm can be used, and if necessary, a photopolymerization initiator is included. Moreover, the combined use of heat by infrared rays, far infrared rays, hot air, high frequency heating or the like is also possible. The proportion of the energy ray curable component, particularly the ultraviolet curable component, in the portion other than the pigment of the ink composition for inkjet printing of the present invention is usually 70 to 95% by weight, typically 80 to 90% by weight. It is. Curing by irradiation with active energy rays can be performed, for example, by placing an irradiation lamp immediately after the discharge nozzle and almost simultaneously with coating. After completing the coating pattern, it is set in the irradiation apparatus. It can also be done.
<アルキレンオキサイド変性ジペンタエリスリトール(メタ)アクリレート>
 本発明のインクジェット印刷用インキ組成物は、架橋性モノマーとして、上記一般式(I)、(II)で表される構造を有するものである。式(I)中、AOは-CH2CH2O-、又は-CH2CH(CH3)O-、又は-CH2CH2CH2CH2O-、又は-CH2CH(C25)O-で表されるアルキレンオキサイド単位を示す。すなわち、エチレンオキサイド(EO)単位、プロピレンオキサイド(PO)単位、及びブチレンオキサイド単位のいずれかを示し、中でも粘度、光感度、重合率という点からはエチレンオキサイド単位であるのが好ましい。これらのアルキレンオキサイド単位は、1種単独で存在していても、2種以上が併存していてもよい。
<Alkylene oxide modified dipentaerythritol (meth) acrylate>
The ink composition for inkjet printing of the present invention has a structure represented by the above general formulas (I) and (II) as a crosslinkable monomer. In the formula (I), AO represents —CH 2 CH 2 O—, —CH 2 CH (CH 3 ) O—, —CH 2 CH 2 CH 2 CH 2 O—, or —CH 2 CH (C 2 H 5 ) An alkylene oxide unit represented by O-. That is, it represents any one of an ethylene oxide (EO) unit, a propylene oxide (PO) unit, and a butylene oxide unit, and among them, an ethylene oxide unit is preferable from the viewpoint of viscosity, photosensitivity, and polymerization rate. These alkylene oxide units may exist individually by 1 type, or 2 or more types may coexist.
 ジペンタエリスリトール1モルあたりの、アルキレンオキサイドの平均付加モル数(L×m)は、0を越えて5以下であり、好ましくは1以上3以下である。アルキレンオキサイドの平均付加モル数が、この範囲より小さいと、架橋モノマーの粘度を低下させる作用、及び、光感度を向上させる作用などが不充分となる。また、この範囲より大きいと、架橋性モノマーの粘度がかえって大きくなり、吐出性を良好にするためには、単官能性(希釈)モノマーの配合量を増やす必要がある。また、アルキレンオキサイド鎖が長くなる分だけ架橋密度も下がるため、硬化物の強度が低下する。一方、付加したアルキレンオキサイド鎖の平均重合度を示すLは0<L≦5であり、好ましくは1≦L≦3である。また、mの平均値は0より大きく6以下であり、1以上、2以下が好ましい。残存する水酸基を示すnの平均値は0以上、6未満であり、1以上、2以下が好ましい。oの平均値は0以上、6以下であり、0以上、4以下が好ましい。これらm、n及びoの合計値は6である。 The average added mole number (L × m) of alkylene oxide per mole of dipentaerythritol is more than 0 and 5 or less, preferably 1 or more and 3 or less. When the average number of added moles of alkylene oxide is smaller than this range, the effect of reducing the viscosity of the crosslinking monomer and the effect of improving the photosensitivity become insufficient. On the other hand, if it is larger than this range, the viscosity of the crosslinkable monomer is increased, and it is necessary to increase the amount of the monofunctional (diluted) monomer in order to improve dischargeability. Moreover, since the crosslink density is lowered by the length of the alkylene oxide chain, the strength of the cured product is lowered. On the other hand, L indicating the average degree of polymerization of the added alkylene oxide chain is 0 <L ≦ 5, preferably 1 ≦ L ≦ 3. Moreover, the average value of m is larger than 0 and 6 or less, and preferably 1 or more and 2 or less. The average value of n indicating the remaining hydroxyl group is 0 or more and less than 6, and preferably 1 or more and 2 or less. The average value of o is 0 or more and 6 or less, and preferably 0 or more and 4 or less. The total value of m, n and o is 6.
 Rは一般式(II)で表される(メタ)アクリロイル基であり、一般式(II)におけるR2は水素原子またはメチル基であり、波線部は結合部を示す。 R is a (meth) acryloyl group represented by the general formula (II), R 2 in the general formula (II) is a hydrogen atom or a methyl group, and a wavy line portion represents a bonding portion.
 すなわち、上記の架橋モノマーは、ジペンタエリスリトールの6個の水酸基の一部又は全部が、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、又はこれらの複数種からなるスペーサーを経て、一般式(II)で表される(メタ)アクリル酸エステル基に変換された構造を有している。そして、(メタ)アクリル酸エステル基を有さない1個、ないしは2個の水酸基が親水性基として残留するため、各種基板などに対する密着性に寄与することができる。 That is, in the crosslinking monomer, part or all of the six hydroxyl groups of dipentaerythritol are represented by the general formula (II) through a spacer composed of ethylene oxide, propylene oxide, butylene oxide, or a plurality of these. It has a structure converted to a (meth) acrylic acid ester group. Since one or two hydroxyl groups having no (meth) acrylic acid ester group remain as hydrophilic groups, it is possible to contribute to adhesion to various substrates.
<アルキレンオキサイド変性ジペンタエリスリトール(メタ)アクリレートの製造方法>
 上記の架橋性モノマーは、例えば以下の方法により製造することができるが、その製造ルートは特に限定されず、どの様な製造方法でも採用することが可能である。
<Method for producing alkylene oxide-modified dipentaerythritol (meth) acrylate>
The crosslinkable monomer can be produced by, for example, the following method, but the production route is not particularly limited, and any production method can be adopted.
 ジペンタエリスリトールを原料とするアルキレンオキサイド変性方法は、任意に選択することができる。一般的な手法としては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等のアルキレンオキサイドを使用した方法に加えて、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の環状カーボネートを使用した方法、エチレンクロロヒドリンを使用した方法が挙げられる。 The alkylene oxide modification method using dipentaerythritol as a raw material can be arbitrarily selected. As a general method, in addition to a method using an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, a method using a cyclic carbonate such as ethylene carbonate, propylene carbonate or butylene carbonate, or ethylene chlorohydrin is used. Method.
 なお、以下に述べる製造方法において、上記の架橋性モノマーの原料として使用する(メタ)アクリル酸化合物は重合性が高いので、製造時や製品保管中に重合が進行しないよう重合禁止剤を適宜使用することができる。重合禁止剤としては、p-ベンゾキノン、ハイドロキノン、ハイドロキノンモノメチルエーテル、2,5-ジフェニルパラベンゾキノンなどのハイドロキノン類、テトラメチルピペリジニル-N-オキシラジカル(TEMPO)などのN-オキシラジカル類、t-ブチルカテコールなどの置換カテコール類、フェノチアジン、ジフェニルアミン、フェニル-β-ナフチルアミンなどのアミン類、クペロン、ニトロソベンゼン、ピクリン酸、分子状酸素、硫黄、塩化銅(II)などを挙げることができる。この中でもハイドロキノン類、フェノチアジンおよびN-オキシラジカル類が汎用性かつ重合抑制効果の点で好ましい。 In the production method described below, since the (meth) acrylic acid compound used as a raw material for the crosslinkable monomer is highly polymerizable, a polymerization inhibitor is appropriately used so that polymerization does not proceed during production or during product storage. can do. Polymerization inhibitors include hydroquinones such as p-benzoquinone, hydroquinone, hydroquinone monomethyl ether and 2,5-diphenylparabenzoquinone, N-oxy radicals such as tetramethylpiperidinyl-N-oxy radical (TEMPO), t -Substituted catechols such as butyl catechol, amines such as phenothiazine, diphenylamine, phenyl-β-naphthylamine, cuperone, nitrosobenzene, picric acid, molecular oxygen, sulfur, copper (II) chloride and the like. Of these, hydroquinones, phenothiazines and N-oxy radicals are preferred from the viewpoints of versatility and polymerization inhibition effect.
 重合禁止剤の添加量は、目的物である一般式(I)で示される化合物に対して、下限がおおよそ10ppm以上、好ましくは30ppm以上であり、上限が、通常5000ppm以下、好ましくは1000ppm以下である。少なすぎる場合は、十分な重合禁止効果が発現せず、製造時や製品保管中に重合が進行する危険性があり、多すぎる場合は、逆に硬化・重合反応を阻害してしまう可能性がある。その為、本発明の化合物単独、またはその重合性樹脂組成物とした際の光感度の低下、硬化物の架橋不良、力学的強度などの物性低下などを引き起こしてしまう恐れがあり、好ましくない。 The addition amount of the polymerization inhibitor is about 10 ppm or more, preferably 30 ppm or more, and the upper limit is usually 5000 ppm or less, preferably 1000 ppm or less with respect to the compound represented by the general formula (I) as the target product. is there. If the amount is too small, there is a risk that polymerization will not sufficiently develop and there is a risk that polymerization will proceed during production or storage of the product, and if it is too large, the curing / polymerization reaction may be hindered. is there. For this reason, the compound of the present invention alone or a polymerizable resin composition thereof may cause reduction in photosensitivity, poor cross-linking of a cured product, and decrease in physical properties such as mechanical strength.
 上記の架橋性モノマーを製造する上での(メタ)アクリル酸エステル基の一般的な導入方法としては、アクリル酸メチル、メタクリル酸メチル等の目的とする構造に対応した(メタ)アクリル酸エステルを使用したエステル交換法、(メタ)アクリル酸クロライドを用いた酸クロライド法、N,N’-ジシクロヘキシルカルボジイミド、2-クロロ-1,3-ジメチルイミダゾリウムクロリド、プロパンホスホン酸無水物、カルボニルジイミダゾール(CDI)、WSCD(水溶性カルボジイミド)などの縮合剤を使用した方法、酸触媒の存在下で(メタ)アクリル酸と共沸・脱水する脱水エステル化法等が挙げられる。以下に代表的なアルキレンオキサイド変性ジペンタエリスリトールのエステル化反応について、製造上可能な条件を記載する。 As a general method for introducing a (meth) acrylic acid ester group in producing the above crosslinkable monomer, a (meth) acrylic acid ester corresponding to a target structure such as methyl acrylate or methyl methacrylate is used. Transesterification method used, acid chloride method using (meth) acrylic acid chloride, N, N′-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolium chloride, propanephosphonic anhydride, carbonyldiimidazole ( CDI), a method using a condensing agent such as WSCD (water-soluble carbodiimide), and a dehydration esterification method in which azeotropic and dehydration with (meth) acrylic acid is performed in the presence of an acid catalyst. The following describes conditions that can be produced for the esterification reaction of typical alkylene oxide-modified dipentaerythritol.
 反応は、(メタ)アクリル酸とアルキレンオキサイド変性ジペンタエリスリトールを酸触媒の存在下、生成する水を留去しながら行うことができる。使用される酸としては、通常のエステル化反応に用いられる酸であれば特に制限なく使用できる。例えば、硫酸や、塩酸などの無機酸、p-トルエンスルホン酸やメタンスルホン酸、カンファースルホン酸などの有機スルホン酸、酸型イオン交換樹脂、フッ素化ホウ素・エーテル錯体などのルイス酸、ランタナイドトリフレートなどの水溶性のルイス酸等が挙げられる。これらの酸は1種単独でも、任意の酸を2種以上混合して用いてもよい。 The reaction can be carried out while distilling off the water produced from (meth) acrylic acid and alkylene oxide-modified dipentaerythritol in the presence of an acid catalyst. Any acid can be used without particular limitation as long as it is an acid used in a normal esterification reaction. For example, inorganic acids such as sulfuric acid and hydrochloric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid, acid type ion exchange resins, Lewis acids such as fluorinated boron and ether complexes, lanthanide trif Examples thereof include water-soluble Lewis acids such as rate. These acids may be used alone or in combination of two or more kinds.
 酸の使用量は、基質であるアルキレンオキサイド変性ジペンタエリスリトールに対して下限が0.1モル当量以上、好ましくは0.5モル当量以上である。一方、上限は制限がないが、通常は20モル等量以下、好ましくは10モル等量以下である。酸触媒量が少なすぎる場合は、反応の進行が遅かったり停止したりするため好ましくなく、また、多すぎる場合には、製品着色や、触媒の残存等の問題が生じたり、マイケル付加物の生成等の好ましくない副反応が起きたりする傾向にある。 The lower limit of the amount of acid used relative to the alkylene oxide-modified dipentaerythritol as a substrate is at least 0.1 molar equivalent, preferably at least 0.5 molar equivalent. On the other hand, the upper limit is not limited, but is usually 20 mol equivalent or less, preferably 10 mol equivalent or less. If the amount of the acid catalyst is too small, the reaction progresses slowly or stops, which is not preferable. On the other hand, if the amount is too large, problems such as product coloring or catalyst remaining may occur, and Michael adduct formation may occur. It tends to cause undesirable side reactions such as
 反応は、溶媒系、無溶媒系のどちらでも行うことができるが、副生物の生成、工程上のハンドリング面から溶剤系が好ましい。溶媒を使用する場合は、特に使用する溶媒に制限はないが、トルエン、キシレンなどの芳香族炭化水素溶媒、ヘキサン、ヘプタンなどの脂肪族炭化水素溶媒、ジエチルエーテル、テトラヒドロフラン、モノエチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルなどのエーテル系溶媒、塩化メチレン、クロロホルム、四塩化炭素等のハロゲン系溶媒などが好適に用いられる。これらの溶媒は1種を単独で用いることもでき、任意の複数の溶媒を混合して使用することもできる。 The reaction can be carried out either in a solvent system or in a solventless system, but a solvent system is preferred from the viewpoint of production of by-products and handling in the process. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol An ether solvent such as dimethyl ether and a halogen solvent such as methylene chloride, chloroform, carbon tetrachloride and the like are preferably used. One of these solvents can be used alone, or a plurality of arbitrary solvents can be mixed and used.
 溶媒を使用する場合、その量は原料であるアルキレンオキサイド変性ジペンタエリスリトールの濃度を、通常は1質量%以上、好ましくは20質量%以上とし、上限は特に制限はないが、通常は80質量%以下、好ましくは70質量%以下とする。反応は、通常は使用する溶媒の沸点以上で行い、生成する水を留去しながら行う。ただし、上記(メタ)アクリル酸クロライドや縮合剤を使用した反応を行う際は、溶剤の沸点以下、もしくは氷冷下で反応を行うことがある。反応時間は任意に選択されるが、生成する水の量、系内の酸価を測定することにより反応の終点を認知することができる。 When a solvent is used, the amount thereof is usually 1% by mass or more, preferably 20% by mass or more, and the upper limit of the concentration of the alkylene oxide-modified dipentaerythritol as a raw material is not particularly limited, but is usually 80% by mass. Hereinafter, it is preferably 70% by mass or less. The reaction is usually carried out at a temperature equal to or higher than the boiling point of the solvent to be used, while distilling off the produced water. However, when the reaction using the (meth) acrylic acid chloride or the condensing agent is performed, the reaction may be performed below the boiling point of the solvent or under ice cooling. The reaction time is arbitrarily selected, but the end point of the reaction can be recognized by measuring the amount of water produced and the acid value in the system.
 反応時間は、下限が通常は30分間以上、好ましくは60分間以上であり、上限は特に限定はされないが通常は20時間以下、好ましくは10時間以下である。 The lower limit of the reaction time is usually 30 minutes or more, preferably 60 minutes or more, and the upper limit is not particularly limited, but is usually 20 hours or less, preferably 10 hours or less.
<精製方法>
 上記の反応により製造された一般式(I)で表される化合物は、従来から用いられている精製方法で特に制限なく精製することができる。例えば、蒸留法、再結晶法、抽出洗浄法、吸着処理法などである。蒸留を行う場合は、その形態としては、単蒸留、精密蒸留、薄膜蒸留、分子蒸留などを任意に選択することができる。
<Purification method>
The compound represented by the general formula (I) produced by the above reaction can be purified without particular limitation by a conventionally used purification method. For example, a distillation method, a recrystallization method, an extraction cleaning method, an adsorption treatment method, and the like. In the case of performing distillation, the form can be arbitrarily selected from simple distillation, precision distillation, thin film distillation, molecular distillation and the like.
<(メタ)アクリル酸エステルモノマーの保存方法>
 上記の架橋性モノマーは、重合性を有しているため、冷暗所に保存することが望ましい。また、重合を防止するために上記した重合禁止剤を上記した量使用して保存することも可能である。
<Storage method of (meth) acrylic acid ester monomer>
Since the crosslinkable monomer has polymerizability, it is desirable to store it in a cool and dark place. It is also possible to store the above-mentioned polymerization inhibitor using the above-mentioned amount in order to prevent polymerization.
<顔料、染料または金属微粉末など>
 本発明のインクジェット印刷用インキ組成物には、着色剤として、顔料または染料を配合することができる。耐候性を得るためには、顔料が好ましく、無機顔料、有機顔料のいずれかまたは両方を使用することができる。また、黒色顔料として、または遮蔽の目的でコンタクト法、ファーネス法、サーマル法などの公知の方法によって製造されたカーボンブラックを配合することができる。さらに、導電性付与のために、各種金属粉末または黒鉛粉末などを配合することができる。
<Pigment, dye or fine metal powder>
In the ink composition for inkjet printing of the present invention, a pigment or a dye can be blended as a colorant. In order to obtain weather resistance, a pigment is preferable, and either or both of an inorganic pigment and an organic pigment can be used. Carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be blended as a black pigment or for the purpose of shielding. Furthermore, various metal powders or graphite powders can be blended for imparting conductivity.
 無機顔料としては、黄鉛、亜鉛黄、紺青、硫酸バリウム、カドミウムレッド、酸化チタン、亜鉛華、ベンガラ、アルミナ、炭酸カルシウム、群青、グラファイト及びチタンブラック等が挙げられる。有機顔料としては、β-ナフトール系、β-オキシナフトエ酸系アニリド系、アセト酢酸アニリド系、ピラゾロン系等の溶性アゾ顔料、β-ナフトール系、β-オキシナフトエ酸系、β-オキシナフトエ酸系アニリド系、アセト酢酸アニリド系モノアゾ、アセト酢酸アニリド系ジスアゾ、ピラゾロン系等の不溶性アゾ顔料、銅フタロシニンブルー、ハロゲン化銅フタロシアニンブルー、スルホン化銅フタロシアニンブルー、金属フリーフタロシアニン等のフタロシアニン系顔料、イソシンドリノン系、キナクリドン系、ジオキサンジン系、ペリノン系及びペリレン系等の多環式又は複素環式化合物が挙げられる。また、黒色顔料としてのカーボンブラックとしては、三菱化学社製のHCF#2650、HCF#2600、HCF#2350、HCF#2300、MCF#1000、MCF#980、MCF#970、MCF#960、MCF88、LFFMA7、MA8、MA11、MA77、MA100、及びデグサ・ヒュルス社製のプリンテックス95、プリンテックス85、プリンテックス75、プリンテックス55、プリンテックス45などが挙げられる。さらに、導電性付与のための金属粉末としては、アルミの微粉末などが挙げられる。 Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine, graphite, and titanium black. Organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetate anilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as sindrinone, quinacridone, dioxazine, perinone, and perylene. Further, as carbon black as a black pigment, HCF # 2650, HCF # 2600, HCF # 2350, HCF # 2300, MCF # 1000, MCF # 980, MCF # 970, MCF # 960, MCF88, manufactured by Mitsubishi Chemical Corporation, Examples include LFFMA7, MA8, MA11, MA77, MA100, and Printex 95, Printex 85, Printex 75, Printex 55, and Printex 45 manufactured by Degussa Huls. Furthermore, examples of the metal powder for imparting conductivity include fine aluminum powder.
 顔料などの粒子径(重量平均粒子径)は、0.01μm~2.0μmが好ましく、より好ましくは0.01μm~1.0μmである。顔料などの配合量は、インクジェット印刷用インキ組成物中、1~60重量%、好ましくは5~40重量%である。顔料を配合する場合、顔料分散剤または顔料誘導体をともに配合するのが好ましく、顔料分散剤としては、具体的には、例えば、イオン性または非イオン性の界面活性剤や、アニオン性、カチオン性またはノニオン性の高分子化合物などが挙げられる。これらの中でも、分散安定性の点から、カチオン性基またはアニオン性基を含む高分子化合物が好ましい。例えば、ポリビニルピロリドン、ポリビニルアルコール、ポリビニルアセタール、ポリアクリル酸、水酸基含有カルボン酸エステル、長鎖ポリアミノアマイドと高分子量酸エステルの塩、高分子量ポリカルボン酸の塩、長鎖ポリアミノアマイドと極性酸エステルの塩、高分子量不飽和酸エステル、高分子共重合物、変性ポリウレタン、変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、芳香族スルホン酸ホルマリン縮合物塩、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンノニルフェニルエーテル、ステアリルアミンアセテートを用いることができる。市場で入手可能な顔料分散剤としては、ルーブリゾール社製のSOLSPERSE、ビックケミー社製のDISPERBYK、エフカアディティブズ社製のEFKAなどが挙げられる。顔料誘導体としては、具体的には、例えば、ジアルキルアミノアルキル基を有する顔料誘導体、ジアルキルアミノアルキルスルホン酸アミド基を有する顔料誘導体などが挙げられる。顔料分散剤などの配合量は、好ましくは、インクジェット印刷用インキ組成物中、0.05~5重量%である。 The particle diameter (weight average particle diameter) of the pigment is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm. The blending amount of the pigment or the like is 1 to 60% by weight, preferably 5 to 40% by weight in the ink composition for ink jet printing. When a pigment is blended, it is preferable to blend a pigment dispersant or pigment derivative together. Specifically, examples of the pigment dispersant include ionic or nonionic surfactants, anionic and cationic surfactants. Alternatively, nonionic polymer compounds can be used. Among these, a polymer compound containing a cationic group or an anionic group is preferable from the viewpoint of dispersion stability. For example, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyacrylic acid, hydroxyl group-containing carboxylic acid ester, salt of long chain polyaminoamide and high molecular weight acid ester, salt of high molecular weight polycarboxylic acid, long chain polyaminoamide and polar acid ester Salt, high molecular weight unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxy Ethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, stearylamine acetate can be used. Examples of commercially available pigment dispersants include Lubrizol's SOLSPERSE, Big Chemie's DISPERBYK, and Fuka Additives' EFKA. Specific examples of the pigment derivative include a pigment derivative having a dialkylaminoalkyl group and a pigment derivative having a dialkylaminoalkylsulfonic acid amide group. The blending amount of the pigment dispersant or the like is preferably 0.05 to 5% by weight in the ink composition for ink jet printing.
 <他のエネルギー線重合性モノマー>
 上記の架橋性モノマーとともに、他の架橋性モノマーを用いることもでき、このような架橋性モノマーとともに、非架橋性モノマーを用いることができる。このように併用する場合、エネルギー線重合性モノマー中における上記の架橋性モノマーの比率を55~90重量%、好ましくは、65~80重量%とすることができる。このように併用するモノマーとしては、エネルギー線の照射時に、共に重合反応を行うものであれば、いずれでも使用可能である。具体的には、炭素数4~30の(メタ)アクリレート類、炭素数5~35の(メタ)アクリルアミド類、炭素数5~35の芳香族ビニル類、炭素数2~20のビニルエーテル類及びその他のラジカル重合性化合物等が挙げられる。この中でも、(メタ)アクリレートまたは(メタ)アクリルアミドが好ましい。なお、本明細書中において、「アクリレート」、「メタクリレート」の双方あるいはいずれかを指す場合「(メタ)アクリレート」という。
<Other energy ray polymerizable monomers>
Other crosslinkable monomers can be used together with the above crosslinkable monomers, and noncrosslinkable monomers can be used together with such crosslinkable monomers. When used in combination, the ratio of the crosslinkable monomer in the energy ray polymerizable monomer can be 55 to 90% by weight, preferably 65 to 80% by weight. As the monomer used in combination, any monomer can be used as long as it undergoes a polymerization reaction when irradiated with energy rays. Specific examples include (meth) acrylates having 4 to 30 carbon atoms, (meth) acrylamides having 5 to 35 carbon atoms, aromatic vinyls having 5 to 35 carbon atoms, vinyl ethers having 2 to 20 carbon atoms, and others. These radically polymerizable compounds are exemplified. Among these, (meth) acrylate or (meth) acrylamide is preferable. In the present specification, the term “(meth) acrylate” refers to both “acrylate” and / or “methacrylate”.
 非架橋性(単官能)の(メタ)アクリレートとしては、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、tert-オクチル(メタ)アクリレート、イソアミル(メタ)アクリレート、デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、4-n-ブチルシクロへキシル(メタ)アクリレート、ボルニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ベンジル(メタ)アクリレート、2-エチルヘキシルジグリコール(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、2-クロロエチル(メタ)アクリレート、4-ブロモブチル(メタ)アクリレート、シアノエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、ブトキシメチル(メタ)アクリレート、メトキシプロピレンモノアクリレート、3-メトキシブチル(メタ)アクリレート、アルコキシメチル(メタ)アクリレート、2-エチルへキシルカルビトール(メタ)アクリレート、アルコキシエチル(メタ)アクリレート、2-(2-メトキシエトキシ)エチル(メタ)アクリレート、2-(2-ブトキシエトキシ)エチル(メタ)アクリレート、2,2,2-テトラフルオロエチル(メタ)アクリレート、1H,1H,2H,2H-パーフルオロデシル(メタ)アクリレート、4-ブチルフェニル(メタ)アクリレート、フェニル(メタ)アクリレート、2,4,5-テトラメチルフェニル(メタ)アクリレート、4-クロロフェニル(メタ)アクリレート、フェノキシメチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート、グリシジロキシブチル(メタ)アクリレート、グリシジロキシエチル(メタ)アクリレート、グリシジロキシプロピル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタアクリレート、4-ヒドロキシブチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、ジエチルアミノプロピル(メタ)アクリレート、トリメトキシシリルプロピル(メタ)アクリレート、トリメトキシシリルプロピル(メタ)アクリレート、トリメチルシリルプロピル(メタ)アクリレート、ポリエチレンオキサイドモノメチルエーテル(メタ)アクリレート、オリゴエチレンオキサイドモノメチルエーテル(メタ)アクリレート、ポリエチレンオキサイド(メタ)アクリレート、オリゴエチレンオキサイド(メタ)アクリレート、オリゴエチレンオキサイドモノアルキルエーテル(メタ)アクリレート、ポリエチレンオキサイドモノアルキルエーテル(メタ)アクリレート、ジプロピレングリコール(メタ)アクリレート、ポリプロピレンオキサイドモノアルキルエーテル(メタ)アクリレート、オリゴプロピレンオキサイドモノアルキルエーテル(メタ)アクリレート、2-メタクリロイロキシエチルコハク酸、2-メタクリロイロキシヘキサヒドロフタル酸、2-メタクリロイロキシエチル-2-ヒドロキシプロピルフタレート、ブトキシジエチレングリコール(メタ)アクリレート、トリフロロエチル(メタ)アクリレート、パーフロロオクチルエチル(メタ)アクリレート、2-ヒドロキシ-3-フェノキシプロピル(メタ)アクリレート、EO変性フェノール(メタ)アクリレート、EO変性クレゾール(メタ)アクリレート、EO変性ノニルフェノール(メタ)アクリレート、PO変性ノニルフェノール(メタ)アクリレート、EO変性-2-エチルヘキシル(メタ)アクリレート等が挙げられる。 Non-crosslinkable (monofunctional) (meth) acrylates include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( (Meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, Anoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) Acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chloro Phenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( Methacrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropylene (Meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide Monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate , Polypropylene oxide monoalkyl ether (meth) acrylate, Ligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, butoxydiethylene glycol (meth) acrylate, Trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol ( And (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified-2-ethylhexyl (meth) acrylate, and the like.
 炭素数5~35の(メタ)アクリルアミド類としては、例えば、(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N-プロピル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド、N-t-ブチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、(メタ)アクリロイルモルフォリンが挙げられる。 Examples of (meth) acrylamides having 5 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and Nn-butyl. (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholine.
<重合開始剤>
 重合開始剤としては、ラジカル重合又はカチオン重合のエネルギー線重合開始剤が挙げられ、例えば、芳香族ケトン類、芳香族オニウム塩化合物、有機過酸化物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物及び活性エステル化合物を有する化合物等が挙げられる。
<Polymerization initiator>
Examples of the polymerization initiator include radical polymerization or cationic polymerization energy beam polymerization initiators, such as aromatic ketones, aromatic onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, ketoxime ester compounds, Examples thereof include compounds having a borate compound, an azinium compound, a metallocene compound, and an active ester compound.
 例えば、アセトフェノン、アセトフェノンベンジルケタール、1-ヒドロキシシクロヘキシルフェニルケトン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、3-メチルアセトフェノン、4-クロロベンゾフェノン、4,4’-ジメトキシベンゾフェノン、4,4’-ジアミノベンゾフェノン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、チオキサントン、ジエチルチオキサントン、2-イソプロピルチオキサントン、2-クロロチオキサントン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパン-1-オン、2-ベンジルー2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1,4-(2-ヒドロキシエトキシ)フェニル-(2-ヒドロキシ-2-プロピル)ケトン、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキシド、オリゴ(2-ヒドロキシ-2-メチル-1-(4-(1-メチルビニル)フェニル)プロパノン)等を挙げることができる。 For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3- Methyl acetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthio Sandton, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like.
 なお、活性エネルギー線による重合開始剤の市販品としては、例えば、チバ・スペシャルティ・ケミカルズ(株)製 商品名:イルガキュア 184、369、651、500、819、907、784、2959、CGI1700、CGI1750、CGI1850、CG24-61、ダロキュア 1116、1173、BASF社製 商品名:ルシリン TPO、UCB社製 商品名:ユベクリル P36、フラテツリ・ランベルティ社製 商品名:エザキュアー KIP150、KIP65LT、KIP100F、KT37、KT55、KTO46、KIP75/B等を挙げることができる。 In addition, as a commercial item of the polymerization initiator by an active energy ray, for example, Ciba Specialty Chemicals Co., Ltd. product name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI1850, CG24-61, DAROCURE 1116, 1173, manufactured by BASF, Inc. Product name: Lucyrin TPO, UCB, Inc. , KIP75 / B and the like.
 活性エネルギー線による重合開始剤の使用量は、公知の重合反応に準じて選択すればよい。例えば、ラジカル重合開始剤は、活性エネルギー線重合性モノマーの総量に対して、通常は0.0001~10重量部、好ましくは0.001~5重量部使用するのが適当である。硬化反応の際の温度は、下限が通常0℃以上、好ましくは10℃以上であり、一方上限は、通常は200℃以下、好ましくは100℃以下である。 The amount of the polymerization initiator used by the active energy ray may be selected according to a known polymerization reaction. For example, the radical polymerization initiator is usually used in an amount of 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on the total amount of the active energy ray polymerizable monomer. The lower limit of the temperature during the curing reaction is usually 0 ° C or higher, preferably 10 ° C or higher, while the upper limit is usually 200 ° C or lower, preferably 100 ° C or lower.
 本発明のインクジェット印刷用インキ組成物は、必要に応じて、5~10重量%の密着性付与剤(シランカップリング剤等)や増感剤、または1~5重量%の溶剤等を含有することができる。更に、使用目的に合わせて、無機微粒子、分散剤、消泡剤、レベリング剤、チクソトロピー性付与剤、スリップ剤、難燃剤、帯電防止剤、酸化防止剤及び紫外線吸収剤等を含有することができる。密着性付与剤としては、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、ビニルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、尿素プロピルトリエトキシシラン、トリス(アセチルアセトネート)アルミニウム及びアセチルアセテートアルミニウムジイソプロピレート等が挙げられる。増感剤としては、ケトクマリン、フルオレン、チオキサントン、ジエチルチオキサントン、イソプロピルチオキサントン、アントラキノン、ナフチアゾリン、ビアセチル、ベンジル及びこれらの誘導体、ペリレン並びに置換アントラセン等が挙げられる。 The ink composition for ink jet printing of the present invention contains 5 to 10% by weight of an adhesion-imparting agent (such as a silane coupling agent) or a sensitizer, or 1 to 5% by weight of a solvent, if necessary. be able to. Furthermore, inorganic fine particles, dispersants, antifoaming agents, leveling agents, thixotropy imparting agents, slip agents, flame retardants, antistatic agents, antioxidants, ultraviolet absorbers, and the like can be contained in accordance with the purpose of use. . Adhesive agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, diethylthioxanthone, isopropylthioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene.
 また、溶剤としては、グリコールエーテル類(エチレングリコールモノアルキルエーテル及びプロピレングリコールモノアルキルエーテル等)、ケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン及びシクロヘキサノン等)、エステル類(エチルアセテート、ブチルアセテート、エチレングリコールアルキルエーテルアセテート及びプロピレングリコールアルキルエーテルアセテート等)、芳香族炭化水素類(トルエン、キシレン、メシチレン及びリモネン等)、アルコール類(メタノール、エタノール、ノルマルプロパノール、イソプロパノール、ブタノール、ゲラニオール、リナロール及びシトロネロール等)及びエーテル類(テトラヒドロフラン及び1,8-シネオール等)が挙げられる。これらは、単独で使用しても2種以上を併用しても良い。 Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol). Alkyl ether acetates and propylene glycol alkyl ether acetates), aromatic hydrocarbons (toluene, xylene, mesitylene, limonene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and And ethers such as tetrahydrofuran and 1,8-cineol. These may be used alone or in combination of two or more.
 本発明のインクジェット印刷用インキ組成物は、場合によっては、インクジェット方式以外の方式にて印刷または塗布を行うのに用いることができる。例えば、スピンコート、ロールコート、スプレーコート等の公知のコーティング法並びに平版印刷、カルトン印刷、金属印刷、オフセット印刷、スクリーン印刷及びグラビア印刷などに用いることができる。 The ink composition for ink jet printing of the present invention can be used for printing or coating by a method other than the ink jet method in some cases. For example, it can be used for known coating methods such as spin coating, roll coating, spray coating, etc., and lithographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing.
 以下、実施例により本発明をさらに詳細に説明するが、本発明はその要旨を超えない範囲内において、以下の実施例によって限定されるものではない。なお、特にことわらない限り、「%」は質量%、「部」は質量基準とする。 Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the following examples within the scope not exceeding the gist thereof. Unless otherwise specified, “%” is based on mass and “part” is based on mass.
<液体クロマトグラフ質量分析(以下、LC-MS分析と略す)条件>
 実施例・比較例のLC-MS分析は次の条件で行った。
[LC部分]Agilent Technologies製 1100シリーズ カラム:Inertsil ODS-2(4.6mmφ×250mm,5μm)、 溶離液:水80.0%-30min→0.0%、メタノール20.0%-30min→100.0%、
 カラム温度:40℃、
 流量:1mL/min、注入量:5μL(200 ppmメタノール溶液)、
 検出器:UV、RI
[MS部分]JMS T100LP(日本電子製)
 リングレンズ電圧:10V、イオン化法:APCI+、脱溶媒室温度:350℃、 ニードル電圧:2500V、オリフィス1温度:80℃、オリフィス1電圧:60V、 イオンガイドピーク間電圧:1000V、オリフィス2電圧:5V
<Conditions for liquid chromatograph mass spectrometry (hereinafter abbreviated as LC-MS analysis)>
LC-MS analysis of Examples and Comparative Examples was performed under the following conditions.
[LC part] 1100 series manufactured by Agilent Technologies Column: Inertsil ODS-2 (4.6 mmφ × 250 mm, 5 μm), eluent: water 80.0% -30 min → 0.0%, methanol 20.0% -30 min → 100 0.0%,
Column temperature: 40 ° C
Flow rate: 1 mL / min, injection amount: 5 μL (200 ppm methanol solution),
Detector: UV, RI
[MS part] JMS T100LP (manufactured by JEOL)
Ring lens voltage: 10 V, ionization method: APCI +, solvent removal chamber temperature: 350 ° C., needle voltage: 2500 V, orifice 1 temperature: 80 ° C., orifice 1 voltage: 60 V, ion guide peak-to-peak voltage: 1000 V, orifice 2 voltage: 5 V
<水酸基価(OH価)測定条件>
 酢酸とピリジンを重量比1:9で混合し、アセチル化試薬とした。サンプルをフラスコに秤量し、アセチル化試薬を加え、80℃で2時間加熱した。反応後、フェノールフタレインを指示薬とし、1mol/l水酸化カリウム水溶液で滴定を行った。
<Measurement conditions for hydroxyl value (OH value)>
Acetic acid and pyridine were mixed at a weight ratio of 1: 9 to obtain an acetylating reagent. The sample was weighed into a flask, an acetylating reagent was added and heated at 80 ° C. for 2 hours. After the reaction, titration was performed with 1 mol / l aqueous potassium hydroxide solution using phenolphthalein as an indicator.
<NMR分析>
 NMR分析の結果は、各ピークの帰属を次式に記載する番号((1)~(3))で示す。
Figure JPOXMLDOC01-appb-C000005
<NMR analysis>
As a result of NMR analysis, assignment of each peak is indicated by a number ((1) to (3)) described in the following formula.
Figure JPOXMLDOC01-appb-C000005
[実施例1](ジペンタエリスリトール3EO付加体アクリレート含有組成物)
<ジペンタエリスリトール3EO付加体アクリレートの合成>
 攪拌装置を備えた容量1Lのオートクレーブ内に、ジペンタエリスリトール(広栄化学工業株式会社製、OH価1324)254g(1.0mol)、トルエン127g、KOH0.3gを仕込み、90℃まで昇温、攪拌し、スラリー状の液体とした。次いで130℃に加熱し、エチレンオキサイド176g(4mol)を徐々にオートクレーブ内に導入し反応せしめた。エチレンオキサイドの導入とともに、オートクレーブ内温度は上昇した。随時冷却を加え、反応温度は140℃以下に保つようにした。反応後、140℃にて水銀柱10mmHg以下にて減圧する事で、過剰のエチレンオキサイド、副生するエチレングリコールの重合体を除去した。その後、酢酸にて中和を行い、pH6~7に調整した。得られたジペンタエリスリトール3EO付加体のOH価は897であった。
[Example 1] (Dipentaerythritol 3EO adduct acrylate-containing composition)
<Synthesis of Dipentaerythritol 3EO Adduct Acrylate>
In a 1 L autoclave equipped with a stirrer, 254 g (1.0 mol) of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., OH number 1324), 127 g of toluene, and 0.3 g of KOH were charged, and the temperature was raised to 90 ° C. and stirred. Thus, a slurry-like liquid was obtained. Next, the mixture was heated to 130 ° C., and 176 g (4 mol) of ethylene oxide was gradually introduced into the autoclave to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and a by-produced ethylene glycol polymer were removed by reducing the pressure at 140 ° C. under 10 mmHg of mercury. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7. The obtained dipentaerythritol 3EO adduct had an OH value of 897.
 得られたエチレングリコール変性ジペンタエリスリトール(OH価897)375g(1mol)、アクリル酸562g(7.8mol)、パラトルエンスルホン酸46g、トルエン900g、ハイドロキノン0.9gをガラス製四つ口フラスコに仕込み、空気を吹き込みながら加熱反応を行った。反応で生じた水はトルエンと共沸する事で系外に随時除去した。反応温度は100~110℃であり、反応終了時に系外へ除去された反応水量は112gであった。反応後、アルカリ水洗、水洗を行い、上層のトルエン層を分離し、トルエンを減圧留去し、一般式(I)、(II)で表される、ジペンタエリスリトール3EO付加体アクリレートを615g(収率88%)得た 375 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH number 897), 562 g (7.8 mol) of acrylic acid, 46 g of paratoluenesulfonic acid, 900 g of toluene, and 0.9 g of hydroquinone are charged into a glass four-necked flask. The heating reaction was performed while blowing air. Water generated by the reaction was removed from the system as needed by azeotroping with toluene. The reaction temperature was 100 to 110 ° C., and the amount of reaction water removed out of the system at the end of the reaction was 112 g. After the reaction, alkaline water washing and water washing are performed, the upper toluene layer is separated, toluene is distilled off under reduced pressure, and 615 g (yield) of dipentaerythritol 3EO adduct acrylate represented by the general formulas (I) and (II) is obtained. (88% rate)
 これにつき、水酸基価の測定、並びに1H-NMR、13C-NMR、HPLC、及びLC-MS、水酸基価による分析を実施したところ、水酸基含有ジペンタエリスリトール2EO付加体アクリレートであることが明らかとなった。以下に、NMR分析、及びLC-MS分析の結果を示し、NMRのピークの帰属は上記番号で示す。 When the hydroxyl value was measured and analyzed by 1 H-NMR, 13 C-NMR, HPLC, LC-MS, and hydroxyl value, it was found that this was a hydroxyl group-containing dipentaerythritol 2EO adduct acrylate. became. The results of NMR analysis and LC-MS analysis are shown below, and the assignment of the NMR peak is indicated by the above number.
<3EO付加体アクリレートの13C-NMR分析(400MHz),in CDCl3
 45ppm:(2)由来、60ppm:(3)由来、61~63ppm:エチレンオキサイドが付加した(3)由来、68~73ppm:(3)に付加したエチレンオキサイド由来、77~79ppm:重クロロホルム由来、128~131ppm:エステル結合したアクリル酸由来、165~167ppm:エステル結合部
< 13 C-NMR analysis of 3EO adduct acrylate (400 MHz), in CDCl 3 >
45 ppm: derived from (2), 60 ppm: derived from (3), 61-63 ppm: derived from (3) added with ethylene oxide, 68-73 ppm: derived from ethylene oxide added to (3), 77-79 ppm: derived from deuterated chloroform, 128 to 131 ppm: derived from ester-bonded acrylic acid, 165 to 167 ppm: ester bond
<3EO付加体アクリレートの1H-NMR分析(400MHz),in CDCl3
 3.3~4.1ppm(16H):(1)、(3)由来、3.6~4.4ppm(8H):(3)のOHに付加したエチレンオキサイド由来、5.7~6.4ppm(18H):アクリル酸エステルの2重結合由来、7.3ppm:重クロロホルム由来
< 1 H-NMR analysis of 3EO adduct acrylate (400 MHz), in CDCl 3 >
3.3 to 4.1 ppm (16H): derived from (1), (3), 3.6 to 4.4 ppm (8H): derived from ethylene oxide added to OH of (3), 5.7 to 6.4 ppm (18H): derived from double bond of acrylate ester, 7.3 ppm: derived from deuterated chloroform
<3EO付加体アクリレートのLC-MS分析>
8.8~11.5分:エチレンオキサイド重合体ジアクリレート、14~16分:ジペンタエリスリトールエチレンオキサイド変性モノアクリレート、16~20分:ジペンタエリスリトールエチレンオキサイド変性ヘキサアクリレート
<LC-MS analysis of 3EO adduct acrylate>
8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate
<顔料分散液の調製>
 酸化チタン[石原産業社製「タイペークR-930」]50部、顔料分散剤[ルーブリゾール社製「ソルスパーズ32000」]5部、N,N-ジエチルアクリルアミド45部[興人(株)製「DEAA」]からなる混合物を、ボールミルを用いて4時間混練することにより顔料濃度50重量%の顔料分散剤液を調製した。
<Preparation of pigment dispersion>
Titanium oxide [Ishihara Sangyo "Typaque R-930"] 50 parts, pigment dispersant [Lubrisol "Solspers 32000"] 5 parts, N, N-diethylacrylamide 45 parts [Kojin Co., Ltd. "DEAA" ]] Was kneaded for 4 hours using a ball mill to prepare a pigment dispersant solution having a pigment concentration of 50% by weight.
<顔料を含有するインク組成物の調製>
 前記顔料分散剤液40部、ジフェニル(2,4,6-トリメチルベンゾイル)フォスフィンオキシド[チバジャパン社製「Irgacure TPO」]3部、ジエチルチオキサントン[日本化薬(株)製「カヤキュアDETX-S」]3部、上記で得られた3EO付加体アクリレート54部をボールミルを用いて25℃で4時間混練して本発明のインクジェット印刷用インク組成物を製造した。
<Preparation of ink composition containing pigment>
40 parts of the pigment dispersant solution, 3 parts of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [“Irgacure TPO” manufactured by Ciba Japan Co., Ltd.], diethylthioxanthone [“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd. ]] 3 parts and 54 parts of the 3EO adduct acrylate obtained above were kneaded at 25 ° C. for 4 hours using a ball mill to produce an ink composition for ink jet printing according to the present invention.
[実施例2](ジペンタエリスリトール4EO付加体アクリレート含有組成物)
<ジペンタエリスリトール4EO付加体アクリレートの合成>
 攪拌装置を備えた容量1Lのオートクレーブ内に、ジペンタエリスリトール(広栄化学工業株式会社製、OH価1324)254g(1.0mol)、トルエン127g、KOH0.3gを仕込み、90℃まで昇温、攪拌し、スラリー状の液体とした。次いで130℃に加熱し、エチレンオキサイド220g(5mol)を徐々にオートクレーブ内に導入し反応せしめた。エチレンオキサイドの導入とともに、オートクレーブ内温度は上昇した。随時冷却を加え、反応温度は140℃以下に保つようにした。反応後、140℃にて水銀柱10mmHg以下にて減圧する事で、過剰のエチレンオキサイド、副生するエチレングリコールの重合体を除去した。その後、酢酸にて中和を行い、pH6~7に調整した。得られたジペンタエリスリトール4EO付加体のOH価は765であった。
[Example 2] (Dipentaerythritol 4EO adduct acrylate-containing composition)
<Synthesis of Dipentaerythritol 4EO Adduct Acrylate>
In a 1 L autoclave equipped with a stirrer, 254 g (1.0 mol) of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., OH number 1324), 127 g of toluene, and 0.3 g of KOH were charged, and the temperature was raised to 90 ° C. and stirred. Thus, a slurry-like liquid was obtained. Next, the mixture was heated to 130 ° C., and 220 g (5 mol) of ethylene oxide was gradually introduced into the autoclave to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and a by-produced ethylene glycol polymer were removed by reducing the pressure at 140 ° C. under 10 mmHg of mercury. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7. The obtained dipentaerythritol 4EO adduct had an OH value of 765.
 得られたエチレングリコール変性ジペンタエリスリトール(OH価765)440g(1mol)、アクリル酸562g(7.8mol)、パラトルエンスルホン酸50g、トルエン900g、ハイドロキノン1gをガラス製四つ口フラスコに仕込み、空気を吹き込みながら加熱反応を行った。反応で生じた水はトルエンと共沸する事で系外に随時除去した。反応温度は100~110℃であり、反応終了時に系外へ除去された反応水量は113gであった。反応後、アルカリ水洗、水洗を行い、上層のトルエン層を分離し、トルエンを減圧留去し、一般式(I)、(II)で表される、ジペンタエリスリトール4EO付加体アクリレートを665g(収率87%)得た。 440 g (1 mol) of the obtained ethylene glycol-modified dipentaerythritol (OH number 765), 562 g (7.8 mol) of acrylic acid, 50 g of paratoluenesulfonic acid, 900 g of toluene, and 1 g of hydroquinone were charged into a glass four-necked flask, and air The reaction was conducted while blowing. Water generated by the reaction was removed from the system as needed by azeotroping with toluene. The reaction temperature was 100 to 110 ° C., and the amount of reaction water removed out of the system at the end of the reaction was 113 g. After the reaction, alkaline water washing and water washing are performed, the upper toluene layer is separated, toluene is distilled off under reduced pressure, and 665 g of dipentaerythritol 4EO adduct acrylate represented by the general formulas (I) and (II) is collected. (Rate 87%).
 これにつき、水酸基価の測定、並びに1H-NMR、13C-NMR、HPLC、及びLC-MS、水酸基価による分析を実施したところ、水酸基含有ジペンタエリスリトール4EO付加体アクリレートであることが明らかとなった。以下に、NMR分析、及びLC-MS分析の結果を示し、NMRのピークの帰属は上記番号で示す。 When the hydroxyl value was measured and analyzed by 1 H-NMR, 13 C-NMR, HPLC, LC-MS, and hydroxyl value, it was found that this was a hydroxyl group-containing dipentaerythritol 4EO adduct acrylate. became. The results of NMR analysis and LC-MS analysis are shown below, and the assignment of the NMR peak is indicated by the above number.
<4EO付加体アクリレートの13C-NMR分析(400MHz),in CDCl3
 45ppm:(2)由来、60ppm:(3)由来、61~63ppm:エチレンオキサイドが付加した(3)由来、68~73ppm:(3)に付加したエチレンオキサイド由来、77~79ppm:重クロロホルム由来、128~131ppm:エステル結合したアクリル酸由来、165~167ppm:エステル結合部
< 13 C-NMR analysis of 4EO adduct acrylate (400 MHz), in CDCl 3 >
45 ppm: derived from (2), 60 ppm: derived from (3), 61-63 ppm: derived from (3) added with ethylene oxide, 68-73 ppm: derived from ethylene oxide added to (3), 77-79 ppm: derived from deuterated chloroform, 128 to 131 ppm: derived from ester-bonded acrylic acid, 165 to 167 ppm: ester bond
<4EO付加体アクリレートの1H-NMR分析(400MHz),in CDCl3
 3.3~4.1ppm(16H):(1)、(3)由来、3.6~4.4ppm(16H):(3)のOHに付加したエチレンオキサイド由来、5.7~6.4ppm(18H):アクリル酸エステルの2重結合由来、7.3ppm:重クロロホルム由来
< 1 H-NMR analysis (400 MHz) of 4EO adduct acrylate, in CDCl 3 >
3.3 to 4.1 ppm (16H): derived from (1) and (3), 3.6 to 4.4 ppm (16H): derived from ethylene oxide added to OH of (3), 5.7 to 6.4 ppm (18H): derived from double bond of acrylate ester, 7.3 ppm: derived from deuterated chloroform
<4EO付加体アクリレートのLC-MS分析>
 8.8~11.5分:エチレンオキサイド重合体ジアクリレート、14~16分:ジペンタエリスリトールエチレンオキサイド変性モノアクリレート、16~20分:ジペンタエリスリトールエチレンオキサイド変性ヘキサアクリレート
<LC-MS analysis of 4EO adduct acrylate>
8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate
<顔料分散液の調製、及び、顔料を含有するインク組成物の調製>
 上記の3EO付加体アクリレートに代えて、得られた4EO付加体アクリレートを用いた他は、実施例1と全く同様に行った。
<Preparation of pigment dispersion and preparation of ink composition containing pigment>
The same procedure as in Example 1 was performed except that the obtained 4EO adduct acrylate was used in place of the above 3EO adduct acrylate.
[実施例3](ジペンタエリスリトール5EO付加体アクリレート含有組成物)
<ジペンタエリスリトール5EO付加体アクリレートの合成>
 攪拌装置を備えた容量1Lのオートクレーブ内に、ジペンタエリスリトール(広栄化学工業株式会社製、OH価1324)254g(1.0mol)、蒸留水36g、KOH0.3gを仕込み、90℃まで昇温、攪拌し、スラリー状の液体とした。次いで130℃に加熱し、エチレンオキサイド264g(6mol)を徐々にオートクレーブ内に導入し反応せしめた。エチレンオキサイドの導入とともに、オートクレーブ内温度は上昇した。随時冷却を加え、反応温度は140℃以下に保つようにした。反応後、140℃にて水銀柱10mmHg以下にて減圧する事で、過剰のエチレンオキサイド、副生するエチレングリコールの重合体を除去した。その後、酢酸にて中和を行い、pH6~7に調整した。得られたジペンタエリスリトール5EO付加体のOH価は706であった。
[Example 3] (Dipentaerythritol 5EO adduct acrylate-containing composition)
<Synthesis of Dipentaerythritol 5EO Adduct Acrylate>
In a 1 L autoclave equipped with a stirrer, 254 g (1.0 mol) of dipentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., OH number 1324), 36 g of distilled water, and 0.3 g of KOH were charged, and the temperature was raised to 90 ° C. The mixture was stirred to obtain a slurry liquid. Next, the mixture was heated to 130 ° C., and 264 g (6 mol) of ethylene oxide was gradually introduced into the autoclave to react. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and a by-produced ethylene glycol polymer were removed by reducing the pressure at 140 ° C. under 10 mmHg of mercury. Thereafter, the mixture was neutralized with acetic acid and adjusted to pH 6-7. The OH value of the obtained dipentaerythritol 5EO adduct was 706.
 得られたエチレングリコール変性ジペンタエリスリトール(OH価706)477g(1mol)、アクリル酸562g(7.8mol)、パラトルエンスルホン酸52g、トルエン900g、ハイドロキノン1gをガラス製四つ口フラスコに仕込み、空気を吹き込みながら加熱反応を行った。反応で生じた水はトルエンと共沸する事で系外に随時除去した。反応温度は100~110℃であり、反応終了時に系外へ除去された反応水量は113gであった。反応後、アルカリ水洗、水洗を行い、上層のトルエン層を分離し、トルエンを減圧留去し、一般式(I)、(II)で表される、ジペンタエリスリトール5EO付加体アクリレートを697g(収率87%)得た。 The obtained ethylene glycol-modified dipentaerythritol (OH number 706) 477 g (1 mol), 562 g (7.8 mol) of acrylic acid, 52 g of paratoluenesulfonic acid, 900 g of toluene and 1 g of hydroquinone were charged into a glass four-necked flask, and air The reaction was conducted while blowing. Water generated by the reaction was removed from the system as needed by azeotroping with toluene. The reaction temperature was 100 to 110 ° C., and the amount of reaction water removed out of the system at the end of the reaction was 113 g. After the reaction, alkaline water washing and water washing are performed, the upper toluene layer is separated, toluene is distilled off under reduced pressure, and 697 g (yield) of dipentaerythritol 5EO adduct acrylate represented by the general formulas (I) and (II) is obtained. (Rate 87%).
 これにつき、水酸基価の測定、並びに1H-NMR、13C-NMR、HPLC、及びLC-MSによる分析を実施したところ、水酸基含有ジペンタエリスリトール5EO付加体アクリレートであることが明らかとなった。以下に、NMR分析、及びLC-MS分析、水酸基価測定の結果を示し、NMRのピークの帰属は上記番号で示す。 When the hydroxyl value was measured and analyzed by 1 H-NMR, 13 C-NMR, HPLC, and LC-MS, it was revealed that it was a hydroxyl group-containing dipentaerythritol 5EO adduct acrylate. The results of NMR analysis, LC-MS analysis and hydroxyl value measurement are shown below, and the assignment of the NMR peak is indicated by the above number.
<5EO付加体アクリレートの13C-NMR分析(400MHz),in CDCl3
 45ppm:(2)由来、60ppm:(3)由来、61~63ppm:エチレンオキサイドが付加した(3)由来、68~73ppm:(3)に付加したエチレンオキサイド由来、77~79ppm:重クロロホルム由来、128~131ppm:エステル結合したアクリル酸由来、165~167ppm:エステル結合部
< 13 C-NMR analysis (400 MHz) of 5EO adduct acrylate, in CDCl 3 >
45 ppm: derived from (2), 60 ppm: derived from (3), 61-63 ppm: derived from (3) added with ethylene oxide, 68-73 ppm: derived from ethylene oxide added to (3), 77-79 ppm: derived from deuterated chloroform, 128 to 131 ppm: derived from ester-bonded acrylic acid, 165 to 167 ppm: ester bond
<5EO付加体アクリレートの1H-NMR分析(400MHz),in CDCl3
 3.3~4.1ppm(16H):(1)、(3)由来、3.6~4.4ppm(24H):(3)のOHに付加したエチレンオキサイド由来、5.7~6.4ppm(18H):アクリル酸エステルの2重結合由来、7.3ppm:重クロロホルム由来
< 1 H-NMR analysis (400 MHz) of 5EO adduct acrylate, in CDCl 3 >
3.3 to 4.1 ppm (16H): derived from (1), (3), 3.6 to 4.4 ppm (24H): derived from ethylene oxide added to OH of (3), 5.7 to 6.4 ppm (18H): derived from double bond of acrylate ester, 7.3 ppm: derived from deuterated chloroform
<5EO付加体アクリレートのLC-MS分析>
 8.8~11.5分:エチレンオキサイド重合体ジアクリレート、14~16分:ジペンタエリスリトールエチレンオキサイド変性モノアクリレート、16~20分:ジペンタエリスリトールエチレンオキサイド変性ヘキサアクリレート
<LC-MS analysis of 5EO adduct acrylate>
8.8 to 11.5 minutes: ethylene oxide polymer diacrylate, 14 to 16 minutes: dipentaerythritol ethylene oxide modified monoacrylate, 16 to 20 minutes: dipentaerythritol ethylene oxide modified hexaacrylate
<顔料分散液の調製、及び、顔料を含有するインク組成物の調製>
 上記の3EO付加体アクリレートに代えて、得られた5EO付加体アクリレートを用いた他は、実施例1と全く同様に行った。
<Preparation of pigment dispersion and preparation of ink composition containing pigment>
The same procedure as in Example 1 was performed except that the obtained 5EO adduct acrylate was used instead of the 3EO adduct acrylate.
[比較例1](ジペンタエリスリトール・ヘキサアクリレート含有組成物)
 上記のジペンタエリスリトール3EO付加体アクリレートに代えて、ジペンタエリスリトール・ヘキサアクリレート(日本化薬株式会社製KAYARAD DPHA)を用いた他は、実施例1と全く同様に行った。
[Comparative Example 1] (Dipentaerythritol / hexaacrylate-containing composition)
The same procedure as in Example 1 was performed except that dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was used in place of the above dipentaerythritol 3EO adduct acrylate.
[比較例2](トリメチロールプロパンアクリレート含有組成物)
 上記のジペンタエリスリトール3EO付加体アクリレートに代えて、トリメチロールプロパンアクリレート(サートマー社製SR351S)を用いた他は、実施例1と全く同様に行った。
[Comparative Example 2] (Trimethylolpropane acrylate-containing composition)
The same procedure as in Example 1 was performed except that trimethylolpropane acrylate (SR351S manufactured by Sartomer) was used in place of the above dipentaerythritol 3EO adduct acrylate.
[比較例3](EO変性トリメチロールプロパントリアクリレート含有組成物)
 上記のジペンタエリスリトール3EO付加体アクリレートに代えて、エチレンオキサイド変性トリメチロールプロパントリアクリレート(サートマー社製SR454)を用いた他は、実施例1と全く同様に行った。
[Comparative Example 3] (EO-modified trimethylolpropane triacrylate-containing composition)
The same procedure as in Example 1 was performed except that ethylene oxide-modified trimethylolpropane triacrylate (SR454 manufactured by Sartomer) was used in place of the dipentaerythritol 3EO adduct.
[比較例4](カプロラクトン変性ジペンタエリスリトールアクリレート含有組成物)
 上記のジペンタエリスリトール3EO付加体アクリレートに代えて、カプロラクトン変性ジペンタエリスリトールアクリレート(日本化薬株式会社製KAYARAD DPCA-60)を用いた他は、実施例1と全く同様に行った。
[Comparative Example 4] (Caprolactone-modified dipentaerythritol acrylate-containing composition)
The same procedure as in Example 1 was performed except that caprolactone-modified dipentaerythritol acrylate (KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.) was used instead of the above-mentioned dipentaerythritol 3EO adduct acrylate.
 上記の実施例1~3、及び比較例1~4のインク組成物についての評価を下記のとおりに行った。 The ink compositions of Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated as follows.
[硬化性]実施例1~3、及び比較例1~4のインク組成物を、易接着処理PETフィルム(東レ株式会社製ルミラーT-60)の易接着処理面にバーコーターを用いて乾燥膜厚10μmにて塗布した。そして、ベルトコンベア式UV照射装置UV照射装置(GSユアサ UVシステム CSN2-40)、及び、スポット式UV照射装置(USHIO Optical Modulex SX-UID500H)にて、積算照度200mj/cm2にて硬化を行った。硬化性の確認は、紫外線照射時にステップタブレット(25段、Riston社製)にて遮光し、タックフリーとなる段数を記載した。段数が高い事は遮光度が高いと言う事を示している。即ち、低い露光量でも硬化可能であり、インク組成物の光感度が高く、生産性に優れると言える。 [Curability] The ink compositions of Examples 1 to 3 and Comparative Examples 1 to 4 were dried using a bar coater on the easy-adhesion-treated surface of an easy-adhesion-treated PET film (Lumirror T-60 manufactured by Toray Industries, Inc.). The coating was applied at a thickness of 10 μm. Then, curing is performed at an integrated illuminance of 200 mj / cm 2 with a belt conveyor type UV irradiation device (GS Yuasa UV system CSN2-40) and spot type UV irradiation device (USHIO Optical Modulex SX-UID500H). It was. For confirmation of curability, light was shielded with a step tablet (25 steps, manufactured by Riston) at the time of ultraviolet irradiation, and the number of steps to be tack-free was described. A high number of steps indicates a high degree of shading. That is, it can be cured even at a low exposure amount, and it can be said that the ink composition has high photosensitivity and excellent productivity.
[耐スチールウール性]易接着処理PETフィルム(東レ株式会社製ルミラーT-60)に、上記硬化性の評価と同様の手法で硬化皮膜を作成した。そして、00番のスチールウールで500gの荷重を掛けて100回研磨した際の塗膜の状態を目視にて観察し、次の基準で評価した。;
 ○:傷なし、△:試験片に10本前後の傷が確認できる、×:多数の傷が確認できる。
[Steel Wool Resistance] A cured film was prepared on an easy-adhesion-treated PET film (Lumilar T-60 manufactured by Toray Industries, Inc.) by the same method as the evaluation of the curability. And the state of the coating film at the time of grind | polishing 100 times with the load of 500g with No. 00 steel wool was observed visually, and the following reference | standard evaluated. ;
◯: No scratch, Δ: Around 10 scratches can be confirmed on the test piece, ×: Many scratches can be confirmed.
[カール性]易接着処理PETフィルム(東レ株式会社製ルミラーT-60)に硬化性の項目と同様の手法で硬化皮膜を作成し、硬化性の項目と同様の手法で硬化皮膜を作成した。平坦な面にフィルムの4隅の一点を固定し、その時の残りの3点の高さを測定し、その平均値をカール性とした。 [Curlability] A cured film was prepared on a PET film (Lumilar T-60 manufactured by Toray Industries, Inc.) by the same method as the curable item, and a cured film was prepared by the same method as the curable item. One point of the four corners of the film was fixed on a flat surface, and the heights of the remaining three points at that time were measured, and the average value was defined as curl.
[吐出性]吐出性評価装置(「インクジェット描画・塗布装置」;マイクロジェット社製NanoPrinter-300)を用いて、吐出性の評価を行った。この評価装置は、ピエゾ素子方式の複数のノズルにより、ヘッド1スキャン分の描画を行うものである。なお、測定室の雰囲気温度は25℃であった。;
 ノズル詰まり無し:○、ノズル詰まり有り:×。
[Dischargeability] Dischargeability was evaluated using a dischargeability evaluation apparatus (“inkjet drawing / coating apparatus”; NanoPrinter-300 manufactured by Microjet). This evaluation apparatus performs drawing for one head scan by a plurality of nozzles of a piezoelectric element method. The atmospheric temperature in the measurement chamber was 25 ° C. ;
No nozzle clogging: ○, Nozzle clogging: ×.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
 表1に示された結果から知られるように、本発明の実施例1~3のインキ組成物であると、ジペンタエリスリトール・ヘキサアクリレートを用いた比較例1に比べて吐出性を改良することができた。これは、適度のエチレンオキシド変性により、架橋性モノマーそのものの粘度を小さくできたためであると考えられた。なお、具体的なデータは示さないが、ジペンタエリスリトールに12モルのエチレンオキシドを付加した同様のアクリレート(ジペンタエリスリトール12EO付加体アクリレート)に比べても、吐出性は大きく改善されていた。また、ジペンタエリスリトールに8モルのエチレンオキシドを付加した同様のアクリレート(ジペンタエリスリトール8EO付加体アクリレート)に比べても、かなりの改善が見られた。 As can be seen from the results shown in Table 1, the ink compositions of Examples 1 to 3 of the present invention have improved ejection properties compared to Comparative Example 1 using dipentaerythritol hexaacrylate. I was able to. This was considered to be because the viscosity of the crosslinkable monomer itself could be reduced by moderate ethylene oxide modification. In addition, although specific data are not shown, the dischargeability was greatly improved as compared with a similar acrylate obtained by adding 12 moles of ethylene oxide to dipentaerythritol (dipentaerythritol 12EO adduct acrylate). In addition, a considerable improvement was seen compared to a similar acrylate obtained by adding 8 mol of ethylene oxide to dipentaerythritol (dipentaerythritol 8EO adduct acrylate).
 比較例2~4では、低粘度であり吐出性に優れた架橋性(多官能)モノマーを用いた結果、吐出性及びカール性では良好であったが、硬化性及び耐スチールウール性が低かった。これと比較した場合、本願各実施例のインキ組成物であると、エチレンオキサイド付加モル数を最低限必要な量にコントロールする事で、耐スチールウール性を維持しつつ、被印刷体上のインキ組成物の硬化収縮による印刷物の変形を抑制する事が可能である事が判った。また、硬化性に関しも、ジペンタエリスリトール・ヘキサアクリレートを用いた比較例1に比べて大きく向上した。硬化性が向上したのは、エチレンオキサイド変性により、末端アクリロイル基の運動性及び自由度が向上するからであると考えられる。なお、具体的なデータは示さないが、ジペンタエリスリトールに12モルのエチレンオキシドを付加した同様のアクリレート(ジペンタエリスリトール12EO付加体アクリレート)に比べても、硬化性及び耐スチールウール性が大きく改善されていた。また、ジペンタエリスリトールに8モルのエチレンオキシドを付加した同様のアクリレート(ジペンタエリスリトール8EO付加体アクリレート)に比べても、かなりの改善が見られた。 In Comparative Examples 2 to 4, as a result of using a crosslinkable (polyfunctional) monomer having a low viscosity and excellent discharge property, the discharge property and curling property were good, but the curability and steel wool resistance were low. . In comparison with this, the ink composition of each Example of the present application is controlled to the minimum required amount of ethylene oxide addition moles, while maintaining the steel wool resistance, the ink on the printing medium It was found that the deformation of the printed matter due to the curing shrinkage of the composition can be suppressed. Further, the curability was greatly improved as compared with Comparative Example 1 using dipentaerythritol hexaacrylate. The reason why the curability is improved is considered that the mobility and the degree of freedom of the terminal acryloyl group are improved by the ethylene oxide modification. Although specific data is not shown, the curability and steel wool resistance are greatly improved compared to the same acrylate (dipentaerythritol 12EO adduct acrylate) obtained by adding 12 moles of ethylene oxide to dipentaerythritol. It was. In addition, a considerable improvement was seen compared to a similar acrylate obtained by adding 8 mol of ethylene oxide to dipentaerythritol (dipentaerythritol 8EO adduct acrylate).
 以上説明した通り、上記一般式(I)及び(II)で示される、アルキレンオキサイド(AO)付加モル数を最適化したアルキレンオキサイド変性ジペンタエリスリトール(メタ)アクリレートを架橋性モノマーとして有する本発明のインクジェット印刷用インキ組成物は、吐出性を良好とする低粘度、良好な光感度及び硬化性、並びに低収縮性を示し、かつ硬化物は良好な耐擦過性を有している。従って、耐水性や堅牢性などが要求される印刷や塗布のためのインクジェット印刷用インキ組成物として好適に用いることができる。また、特には、プリント配線基板などの電気回路製品の製造に好適に用いることができ、例えば配線形成後の所定の箇所での絶縁膜の形成や、蒸着・スパッタリングなどのためのレジストパターンの形成などに用いることができる。 As described above, according to the present invention, the alkylene oxide-modified dipentaerythritol (meth) acrylate represented by the above general formulas (I) and (II) and having an optimized number of added moles of alkylene oxide (AO) is used as a crosslinkable monomer. The ink composition for ink-jet printing exhibits low viscosity for good dischargeability, good photosensitivity and curability, and low shrinkage, and the cured product has good scratch resistance. Therefore, it can be suitably used as an ink composition for ink jet printing for printing or coating requiring water resistance and fastness. In particular, it can be suitably used for the manufacture of electrical circuit products such as printed wiring boards. For example, formation of an insulating film at a predetermined position after wiring formation, formation of a resist pattern for vapor deposition / sputtering, etc. Can be used.

Claims (2)

  1.  下記一般式(I)及び(II)で表される構造を有するアルキレンオキサイド変性ジペンタエリスリトール(メタ)アクリレートを含有することを特徴とするインクジェット印刷用インキ組成物。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
     但し、一般式(I)中、Rは一般式(II)で表される置換基を表し、AOは-CH2CH2O-、-CH2CH(CH3)O-、-CH2CH2CH2CH2O-、又は-CH2CH(C25)O-で表されるアルキレンオキサイド単位の中から選択された1種又は2種以上を示し、付加したアルキレンオキサイド鎖の平均重合度を示すLは0<L≦5であり、mの平均値は0より大きく5以下であり、アルキレンオキサイドの平均付加モル数L×mは0<L×m≦5であり、nは1もしくは2、oの平均値は0以上6以下であり、m、n及びoの合計値は6である。一般式(II)中、R2は水素原子又はメチル基を示す。
    An ink composition for ink-jet printing comprising an alkylene oxide-modified dipentaerythritol (meth) acrylate having a structure represented by the following general formulas (I) and (II).
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    In general formula (I), R represents a substituent represented by general formula (II), and AO represents —CH 2 CH 2 O—, —CH 2 CH (CH 3 ) O—, —CH 2 CH 1 represents one or more selected from alkylene oxide units represented by 2 CH 2 CH 2 O— or —CH 2 CH (C 2 H 5 ) O—, and represents the average of added alkylene oxide chains L indicating the degree of polymerization is 0 <L ≦ 5, the average value of m is greater than 0 and 5 or less, the average added mole number L × m of alkylene oxide is 0 <L × m ≦ 5, and n is The average value of 1 or 2, o is 0 or more and 6 or less, and the total value of m, n, and o is 6. In the general formula (II), R 2 represents a hydrogen atom or a methyl group.
  2.  ジペンタエリスリトール1モルあたりのアルキレンオキサイドの平均付加モル数(L×m)が3~5であることを特徴とする請求項1に記載のインクジェット印刷用インキ組成物。 2. The ink composition for ink jet printing according to claim 1, wherein an average added mole number of alkylene oxide per mole of dipentaerythritol (L × m) is 3 to 5.
PCT/JP2014/054116 2013-03-01 2014-02-21 Ink composition for inkjet printing WO2014132881A1 (en)

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