WO2022202807A1 - Layered body and primer composition - Google Patents

Layered body and primer composition Download PDF

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Publication number
WO2022202807A1
WO2022202807A1 PCT/JP2022/013131 JP2022013131W WO2022202807A1 WO 2022202807 A1 WO2022202807 A1 WO 2022202807A1 JP 2022013131 W JP2022013131 W JP 2022013131W WO 2022202807 A1 WO2022202807 A1 WO 2022202807A1
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silicone
layer
primer layer
primer
group
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PCT/JP2022/013131
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French (fr)
Japanese (ja)
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はるか 小名
憲一 江口
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日東電工株式会社
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Publication of WO2022202807A1 publication Critical patent/WO2022202807A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to laminates, and more particularly, laminates used to prevent snow and ice from adhering to surfaces of objects such as solar panels, aircraft, railroads, automobiles, wind power generators, houses, traffic lights, signboards, etc. Regarding.
  • the present invention also relates to a primer composition capable of forming a primer layer in the laminate.
  • snow accretion and freezing on residential roofs, signboards, etc. can cause damage to these structures and injury to people due to falling snow.
  • Patent Document 1 discloses that at least part of a silicone polymer in a composition for forming an undercoat layer contains a polar group. Techniques for attaching substituents are disclosed.
  • Patent Document 1 has room for further improvement in the adhesion between the layers in the laminate.
  • the present invention has been made in view of the above-mentioned conventional circumstances, and the object of the present invention is to provide a laminate having excellent adhesion between layers and excellent anti-icing and/or anti-snowing function. It is an issue.
  • the inventors of the present invention have made intensive studies to solve the above problems, and as a result, have focused on the resin in the silicone layer of the laminate, and have completed the present invention.
  • the present invention relates to the following ⁇ 1> to ⁇ 9>.
  • a laminate having a silicone layer and a primer layer The silicone layer contains an oil component and an addition-type silicone resin, The oil component can exude from the silicone layer when the temperature drops below a predetermined value,
  • the silicone layer contains a curing catalyst.
  • ⁇ 4> The laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the primer composition forming the primer layer contains a curing catalyst.
  • ⁇ 5> The laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the primer composition forming the primer layer contains a hydrosilyl group-containing curing agent.
  • ⁇ 6> The laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the base polymer has an SP value of 7.5 to 11.0 (cal/cm 3 ) 1/2 .
  • ⁇ 7> The laminate according to any one of ⁇ 1> to ⁇ 6>, further comprising a substrate.
  • ⁇ 8> Containing a base polymer having an SP value of 7.5 to 11.0 (cal/cm 3 ) 1/2 , A primer composition containing at least one selected from the group consisting of a hydrosilyl group-containing curing agent and a curing catalyst.
  • the primer composition according to ⁇ 8> which has a functional group capable of reacting with the hydrosilyl group-containing curing agent.
  • the laminate of the present invention has excellent adhesion between layers and has excellent anti-icing and/or anti-snowing properties.
  • FIG. 1 is a cross-sectional view showing an example of a layer structure including the laminate of the present invention.
  • the laminate of the present invention has a silicone layer and a primer layer.
  • the silicone layer contains an oil component and an addition-type silicone resin.
  • the oil component can exude from the silicone layer when the temperature drops below a predetermined value.
  • a predetermined value means, for example, the freezing point (0° C.) or lower.
  • oil component for example, silicone oil, hydrocarbon oil, fluorine oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, alcohol, etc. can be used.
  • silicone oils examples include silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF -56A, KF-6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Co., Ltd.
  • silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. e.g., KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF -56A, KF-6000, KF-6001, KF-6002, KF-6003, etc.
  • the silicone layer contains an addition-type silicone resin.
  • the addition-type silicone resin and the base polymer in the primer layer are bonded, and the adhesion between the silicone layer and the primer layer is improved.
  • the addition-type silicone resin means a resin polymerized by an addition reaction obtained by curing a silicone resin having an unsaturated group (carbon-carbon double bond) with a curing agent.
  • Examples of unsaturated groups in silicone resins having unsaturated groups (carbon-carbon double bonds) include vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, and hexenyl groups.
  • a vinyl group is preferable from the viewpoint of improving the adhesion between the silicone layer and the primer layer.
  • silicone resins having unsaturated groups include those whose main chain is a repeating unit of diorganosiloxane and whose terminal is a triorganosiloxane structure, and those having a branched or cyclic structure.
  • organo groups bonded to silicon in terminals and repeating units include methyl, ethyl, and phenyl groups. Specific examples include methylpolysiloxane having vinyl groups at both ends.
  • silicone resins having specific unsaturated groups include KE-1310ST, KE-1935A/KE-1935B, KE-1950A/KE-1950B manufactured by Shin-Etsu Chemical Co., Ltd., KE-103, KE-1316, KE-1600, KE-1606, KE-1204A/KE-1204B and the like.
  • the curing agent preferably contains hydrosilyl groups (SiH groups), and more preferably contains two or more hydrosilyl groups at the terminals and/or in the repeating structure.
  • the curing agent is exemplified by a repeating unit of diorganosiloxane as a main chain and a triorganosiloxane structure as a terminal, and may have a branched or cyclic structure.
  • Silicon-bonded organo groups in terminals and repeating units are exemplified by methyl, ethyl, octyl, and phenyl groups, and curing agents in which two or more of these groups are substituted with hydrogen are preferred. Specific examples include hydrogen silicone and the like.
  • Examples of specific curing agents include cat-1310s, KF-99, and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., HMS-151, HMS-301, and HMS-501 manufactured by Gelest.
  • the reaction between the silicone resin having an unsaturated group (carbon-carbon double bond) and the curing agent is preferably carried out in the presence of a curing catalyst. That is, the silicone layer preferably contains a curing catalyst.
  • curing catalysts examples include platinum catalysts.
  • the primer layer contains a base polymer that bonds with the addition-type silicone resin in the silicone layer, resulting in improved adhesion between the silicone layer and the primer layer.
  • the SP value of the base polymer is preferably 7.5 to 11.0 (cal/cm 3 ) 1/2 .
  • the SP value of the base polymer is within the above range, it is possible to prevent the oil component in the silicone layer from migrating to the primer layer, thereby preventing a decrease in strength due to swelling of the primer layer.
  • the SP value of the base polymer is more preferably 7.6 to 10.9 (cal/cm 3 ) 1/2 , more preferably 7.8 to 10.7 (cal/cm 3 ) 1 from the viewpoint of preventing migration of oil components. /2 is more preferable, and 8.0 to 10.5 (cal/cm 3 ) 1/2 is particularly preferable.
  • the SP value can be measured by the method described in Examples.
  • the curing agent used in the curing reaction of the addition-type silicone resin is preferably a hydrosilyl group-containing curing agent
  • the base polymer in the primer layer is the hydrosilyl It is preferably bonded to the addition-type silicone resin via a structural unit derived from the group-containing curing agent.
  • base polymers include thermosetting elastomers such as acrylic rubber and diene rubber, SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), SEPS (styrene- ethylene-propylene-styrene block copolymer), SBR (styrene-butadiene rubber), SEBS (styrene-ethylene-butylene-styrene block copolymer) and other styrene thermoplastic elastomers, polymethyl methacrylate and acrylic acid alkyl ester block copolymer (thermoplastic acrylic elastomer), EPDM (ethylene propylene diene rubber), EPT (ethylene propylene rubber), PE (polyethylene), PP (polypropylene), and the like.
  • SEBS is preferable from the viewpoint of improving the adhesion between the silicone layer and the primer layer.
  • the base polymer preferably has a functional group.
  • the functional group bonds with the addition-type silicone resin in the silicone layer, improving the adhesion between the silicone layer and the primer layer.
  • Examples of the functional group include linear, branched, or cyclic alkenyl groups (isopropenyl group, vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1- cyclopentenyl group, 1-cyclohexenyl group, etc.), amino group, carboxyl group, hydroxyl group, epoxy group, silanol group, maleic acid group and the like.
  • a vinyl group and an isopropenyl group are preferable, and an isopropenyl group is more preferable, from the viewpoint of improving the adhesion between the silicone layer and the primer layer.
  • a primer layer is formed from a primer composition.
  • the primer composition preferably contains the curing catalyst described above in addition to the base polymer described above.
  • the functional groups of the primer composition are more likely to react with the functional groups of the silicone layer, thereby improving the adhesion between the silicone layer and the primer layer.
  • the primer composition preferably contains the above-mentioned hydrosilyl group-containing curing agent in addition to the above-mentioned base polymer.
  • the primer layer bonds with the addition-type silicone resin in the silicone layer via structural units derived from the hydrosilyl group-containing curing agent, and the adhesion between the silicone layer and the primer layer is improved. do.
  • the primer composition may further contain a blend polymer that does not bond with the addition-type silicone resin in the silicone layer.
  • the inclusion of the blend polymer improves the adhesion between the substrate and the primer layer.
  • blend polymers include thermosetting elastomers such as acrylic rubber and diene rubber, SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), SEPS (styrene- ethylene-propylene-styrene block copolymer), SBR (styrene-butadiene rubber), SEBS (styrene-ethylene-butylene-styrene block copolymer) and other styrene thermoplastic elastomers, polymethyl methacrylate and acrylic acid alkyl ester block copolymer (thermoplastic acrylic elastomer), EPDM (ethylene propylene diene rubber), EPT (ethylene propylene rubber), PE (polyethylene), PP (polypropylene), and the like.
  • SEBS is preferable from the viewpoint of improving the adhesion between the substrate and the primer layer.
  • the blend polymer preferably has a functional group.
  • a functional group in the blend polymer By having a functional group in the blend polymer, the interaction between the functional group and the base material is strengthened, and the adhesion between the base material and the primer layer is improved.
  • Examples of the functional group include linear, branched, or cyclic alkenyl groups (isopropenyl group, vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1- cyclopentenyl group, 1-cyclohexenyl group, etc.), amino group, carboxyl group, hydroxyl group, epoxy group, silanol group, maleic acid group and the like.
  • a maleic acid group and an amino group are preferable from the viewpoint of improving the adhesion between the substrate and the primer layer.
  • the laminate of the present invention can be obtained, for example, by forming a primer layer 11 on a substrate 13 and forming a silicone layer 12 thereon, as shown in FIG.
  • the primer composition that forms the primer layer is applied to the base material by general methods such as brushing, spray coating, and various coater coatings. Coating is usually carried out 1-2 times.
  • the primer composition for forming the primer layer can be obtained by mixing and/or stirring each component by a known method.
  • the thickness of the primer layer is not particularly limited, it is preferably 10-500 ⁇ m, more preferably 30-200 ⁇ m.
  • base materials include polyurethane resins, polyurethane acrylic resins, rubber resins, vinyl chloride resins, polyester resins, silicone resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, ABS, AES, AS, ionomer, etc.), metal plates or foils (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can also be used.
  • the primer composition After coating the substrate with the primer composition that forms the primer layer, the primer composition can be cured or dried by standing for 3 minutes to 3 hours, for example, in an environment of -10 to 180°C. can.
  • a silicone composition that forms a silicone layer is applied to the primer layer by a general method such as brush coating, spray coating, and various coater coatings. Coating is usually carried out 1-2 times.
  • the silicone composition forming the silicone layer can be obtained by mixing and/or stirring each component by a known method.
  • the thickness of the silicone layer is not particularly limited, but is preferably 500 ⁇ m or less so that the oil component can easily permeate to the surface of the silicone layer, in other words, to ensure oil permeability to the silicone layer. From the viewpoint of strength, the thickness is preferably 50 ⁇ m or more.
  • the silicone composition After coating the primer layer with the silicone composition that forms the silicone layer, the silicone composition is cured or dried by allowing it to stand in an environment of, for example, ⁇ 10 to 180° C. for, for example, 3 minutes to 7 days, followed by lamination. you can get a body
  • the curing or drying of the primer composition forming the primer layer and the curing or drying of the silicone composition forming the silicone layer may be carried out simultaneously or separately.
  • the primer composition forming the primer layer and the silicone composition forming the silicone layer may contain an inorganic filler such as silica.
  • silica for example, silica manufactured by Nippon Aerosil Co., Ltd. (e.g., AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, R9200) and the like can be used. can be done.
  • the content of the oil component in the silicone layer can be set to preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Also, the content of the oil component can be set to preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
  • the content of the addition-type silicone resin in the silicone layer can be set to preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. Also, the content of the addition-type silicone resin can be set to preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
  • the content of the curing catalyst in the silicone layer can be set to preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.0005% by mass or more. Also, the content of the curing catalyst can be set to preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of the base polymer in the primer layer can be set to preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Also, the content of the base polymer can be set to preferably 100% by mass or less, more preferably 99.99% by mass or less, and even more preferably 99.98% by mass or less.
  • the content of the curing catalyst in the primer layer can be set to preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.0005% by mass or more. Also, the content of the curing catalyst can be set to preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of the hydrosilyl group-containing curing agent in the primer layer can be set to preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more. Also, the content of the hydrosilyl group-containing curing agent can be set to preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
  • the content of the blend polymer in the primer layer can be set to preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. Also, the content of the blend polymer can be set to preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • primer layer As primer layer components, base polymer: Hybler 5127 (manufactured by Kuraray Co., Ltd.), curing (crosslinking) agent: hydrogen siloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-9901), curing catalyst (Shin-Etsu Chemical Co., Ltd. product, product number: CAT-PL-50T).
  • base polymer Hybler 5127 (manufactured by Kuraray Co., Ltd.)
  • curing (crosslinking) agent hydrogen siloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-9901)
  • curing catalyst Shin-Etsu Chemical Co., Ltd. product, product number: CAT-PL-50T.
  • a base polymer was dissolved in toluene to prepare a toluene solution with a base polymer content of 20% by mass.
  • the toluene solution 99.2% by mass
  • hydrogensiloxane oil (0.6% by mass)
  • curing catalyst (0.2% by mass) were mixed under conditions of 25° C. and 101 kPa.
  • the resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a primer composition.
  • the primer composition is applied to a PET (polyethylene terephthalate) film (Lumirror (registered trademark) 75-S10 manufactured by Toray Industries, Inc.) using a baker applicator (YBA type 5 manufactured by Yoshimitsu Seiki Co., Ltd.) to a thickness of 200 ⁇ m, A primer layer was formed by drying (evaporating toluene) in an environment of 25° C. for 30 minutes.
  • PET polyethylene terephthalate
  • YBA type 5 manufactured by Yoshimitsu Seiki Co., Ltd.
  • silicone layer components resin component (room temperature curing type): KE-1310ST (manufactured by Shin-Etsu Chemical Co., Ltd., silicone resin having a vinyl group, containing silica), curing agent (manufactured by Shin-Etsu Chemical Co., Ltd., product number: cat-1310s , hydrogen silicone, containing platinum catalyst), first oil component (compatible oil): dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-96 (50cs)), second oil component (incompatible oil ): Carbinol oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6002) and a curing catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., product number: CAT-PL-50T) were prepared.
  • first oil component compatible oil
  • dimethylsiloxane oil manufactured by Shin-Etsu Chemical Co., Ltd.
  • a resin component (47.4% by mass), a first oil component (21.3% by mass), and a second oil component (26.1% by mass) were mixed under conditions of 25°C and 101 kPa.
  • the resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds, and then stirred with a Disper (Labo Solution, manufactured by Primix Co., Ltd.) at a speed of 2000 rpm for 5 minutes.
  • a curing agent (4.7% by mass) and a curing catalyst (0.5% by mass) were added and stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a silicone composition.
  • the silicone composition was applied on the above-described primer layer with a baker applicator (YBA type 5 manufactured by Yoshimitsu Seiki Co., Ltd.) to a thickness of 500 ⁇ m, and cured in an environment of 25° C. for 1 week to form a laminate. .
  • a baker applicator YBA type 5 manufactured by Yoshimitsu Seiki Co., Ltd.
  • Example 2 (primer layer) A primer layer was formed in the same manner as in Example 1 except that hydrogensiloxane oil and curing catalyst were not used.
  • Example 2 (Silicone layer and laminate) In addition to the components used in Example 1, phenyl oil (manufactured by Momentive, product number: TSF-437) was prepared as a second oil component, and hydrogensiloxane oil (Shin-Etsu Chemical Co., Ltd.) was additionally used as a curing (crosslinking) agent. Co., Ltd., product number: KF-9901) was prepared.
  • a resin component (46.7% by mass), a first oil component (20.6% by mass), a second oil component (26.1% by mass), and a curing (crosslinking) agent (1.4% by mass) were heated at 25°C. , 101 kPa.
  • the resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds, and then stirred with a Disper (Labo Solution, manufactured by Primix Co., Ltd.) at a speed of 2000 rpm for 5 minutes.
  • a curing agent (4.7% by mass) and a curing catalyst (0.5% by mass) were added and stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a silicone composition.
  • a laminate was formed by coating and curing the silicone composition on the primer layer described above in the same manner as in Example 1.
  • Example 3 (primer layer) The same operation as in Example 1 was performed to form a primer layer.
  • Example 4 (primer layer) The same operation as in Example 1 was performed to form a primer layer.
  • silicone layer component a silicone resin (silicone resin having a vinyl group, hydrogen silicone and platinum catalyst), first oil component (compatible oil): dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-96 (50cs)), second oil component (incompatible oil): carbinol An oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6002) was prepared.
  • first oil component compatible oil
  • dimethylsiloxane oil manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-96 (50cs)
  • second oil component incompatible oil
  • carbinol An oil manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6002
  • a silicone composition was obtained in the same manner as in Example 1, except that the content of each component was as shown in Table 2.
  • a laminate was formed by applying the silicone composition to a thickness of 500 ⁇ m on the above primer layer and drying at 150° C. for 10 minutes.
  • Example 5 A primer layer was formed in the same manner as in Example 1, except that the components and contents of the primer composition were as shown in Table 1.
  • primer layer A primer layer was formed in the same manner as in Example 1, except that the components and contents of the primer composition were as shown in Table 1.
  • "Kraton FG1901GT” shown in Table 1 is maleic anhydride-modified SEBS manufactured by Kraton Polymer.
  • Example 2 (Silicone layer and laminate) The same operation as in Example 1 was performed to form a silicone layer and a laminate.
  • Example 7 A primer layer was formed in the same manner as in Example 1, except that the components and contents of the primer composition were as shown in Table 1.
  • “Tuftech MP10" described in Table 1 is an amine-modified SEBS manufactured by Asahi Kasei Corporation.
  • Example 2 (Silicone layer and laminate) The same operation as in Example 1 was performed to form a silicone layer and a laminate.
  • Primer layer As a primer layer component, a base polymer: Septon 8007L (manufactured by Kuraray Co., Ltd.) was prepared.
  • a base polymer was dissolved in toluene to prepare a toluene solution with a base polymer content of 20% by mass.
  • the toluene solutions were mixed under conditions of 25° C. and 101 kPa.
  • the resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a primer composition.
  • a primer layer was formed from the primer composition by performing the same operation as in Example 1.
  • siliconeone layer and laminate A silicone composition was obtained in the same manner as in Example 1, except that the components and contents of the silicone composition were as shown in Table 2.
  • siliconeone layer and laminate A silicone composition was obtained in the same manner as in Example 1, except that the components and contents of the silicone composition were as shown in Table 2.
  • Primer layer A primer layer was formed in the same manner as in Comparative Example 1, except that the components and contents of the primer composition were as shown in Table 1.
  • Primer layer A primer layer was formed in the same manner as in Comparative Example 1, except that the components and contents of the primer composition were as shown in Table 1.
  • SP value solubility parameter
  • the SP value (solubility parameter) of the base polymer of the primer layer is calculated from the cohesive energy E and molar molecular volume V described in the paper (R. F. Fedors: Polym. Eng. Sci., 14 [2], 147-154 (1974)). It was obtained from the Fedors method using
  • the SP value was obtained by dividing the total cohesive energy ⁇ E of the entire molecule of the target substance by the total molar molecular volume ⁇ V of the entire molecule of the target substance and taking the square root.
  • the total cohesive energy ⁇ E of the entire molecule of the target substance can be obtained by taking the weighted average of the cohesive energies E (cal/mol) of the respective atomic groups described in the above paper by molar ratio.
  • the total molar molecular volume ⁇ V of the entire molecule of the target substance can be obtained by weighting the molar molecular volume V (cm 3 /mol) of each atomic group described in the above paper and averaging the molar ratio.
  • the molar ratio of each constituent atomic group of the substance of interest can be determined by performing Fourier transform nuclear magnetic resonance spectroscopy analysis.
  • Adhesion (adhesion) property was evaluated with reference to JISK-5600-5-6 (mechanical properties of coating film adhesion property). Specifically, a crosscut test cutter guide (trade name “Super Cutter Guide”, manufactured by Taiyu Kizai Co., Ltd.), a cutter, a polyimide adhesive tape (NO.360UL, thickness 0.06 mm ⁇ width 50 mm, manufactured by Nitto Denko Corporation) prepared.
  • the polyimide adhesive tape uses a silicone adhesive and was selected because of its high adhesion to the silicone layer.
  • a transparent adhesive tape cut to a length of about 75 mm was pasted on the part cut into the lattice, and then rubbed firmly with a finger to stick. (The tape was rubbed flat with a finger over the portion of the grid and a minimum length of 20 mm). Proper contact of the tape to the coating was judged by the color of the coating seen through the tape.
  • Adhesion evaluation was performed according to JIS K5600-5-6, and evaluation was performed in six stages from 0 to 5, with 0 to 1 classified as ⁇ (good) and 2 to 5 classified as ⁇ (poor). Table 3 shows the results.
  • the laminate of the present invention has excellent adhesion between the primer layer and the silicone layer, and has an excellent anti-icing and/or anti-snowing function.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention pertains to a layered body that includes a silicone layer and a primer layer. The silicone layer contains an oil component and an addition-type silicone resin. The oil component can exude from the silicone layer when the temperature drops to a prescribed value or less. The primer layer contains a base polymer that bonds to the addition-type silicone resin.

Description

積層体及びプライマー組成物Laminate and primer composition
　本発明は、積層体に関し、詳しくは、太陽光パネル、航空機、鉄道、自動車、風力発電機、住宅、信号機、看板等の物体表面への雪や氷の付着を防止するために用いられる積層体に関する。また、本発明は、当該積層体中のプライマー層を形成することができるプライマー組成物に関する。 TECHNICAL FIELD The present invention relates to laminates, and more particularly, laminates used to prevent snow and ice from adhering to surfaces of objects such as solar panels, aircraft, railroads, automobiles, wind power generators, houses, traffic lights, signboards, etc. Regarding. The present invention also relates to a primer composition capable of forming a primer layer in the laminate.
　物体表面への氷の付着（着氷）や降雪による雪片の付着（着雪）は、様々な分野において多くの被害や障害をもたらす原因となっている。例えば、航空機翼への着氷、機関車下部への着雪・凍結、自動車のヘッドライトへの着雪、太陽光パネルや風力発電機のブレードへの着氷、信号機の灯器への着雪・凍結等は、これらの運行、運転、安全性に対する障害となり得る。
　また、住宅屋根や看板等への着雪・凍結は、これらの構築物の損傷や落雪による人への被害の原因となり得る。 Adhesion of ice to the surface of objects (icing) and adhesion of snowflakes due to snowfall (snow accretion) cause many damages and obstacles in various fields. For example, icing on aircraft wings, snow accumulating on locomotives, snow accumulating on automobile headlights, icing on solar panels and blades of wind power generators, and snow accumulating on traffic lights.・Freezing, etc., can become an obstacle to these operations, driving, and safety.
In addition, snow accretion and freezing on residential roofs, signboards, etc. can cause damage to these structures and injury to people due to falling snow.
　従来、各産業分野において、このような物体表面への着雪や着氷を防止するための対策として、オイルを含有する様々な積層体が開発されている。また、積層体中の各層間の密着性を向上させることが望まれている。 Conventionally, in various industrial fields, various oil-containing laminates have been developed as measures to prevent snow and ice from accumulating on the surface of objects. Moreover, it is desired to improve the adhesion between each layer in the laminate.
　積層体中の各層間の密着性を向上させる技術として、例えば、特許文献１では、下塗層を形成する下塗層形成用組成物中のシリコーン重合体の少なくとも一部に、極性基を含む置換基を結合させる技術が開示されている。 As a technique for improving the adhesion between layers in a laminate, for example, Patent Document 1 discloses that at least part of a silicone polymer in a composition for forming an undercoat layer contains a polar group. Techniques for attaching substituents are disclosed.
日本国特開２０１９－１７３０１２号公報Japanese Patent Application Laid-Open No. 2019-173012
　しかしながら、本発明者らの検討によると、特許文献１に記載の技術では、積層体中の各層間の密着性にさらなる向上の余地があることがわかった。 However, according to the studies of the present inventors, it was found that the technique described in Patent Document 1 has room for further improvement in the adhesion between the layers in the laminate.
　本発明は、上記従来の実情に鑑みてなされたものであって、各層間の密着性に優れ、かつ優れた着氷及び／又は着雪防止機能を有する積層体を提供することを解決すべき課題としている。 The present invention has been made in view of the above-mentioned conventional circumstances, and the object of the present invention is to provide a laminate having excellent adhesion between layers and excellent anti-icing and/or anti-snowing function. It is an issue.
　本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、積層体が有するシリコーン層中の樹脂に着目し、本発明を完成するに至った。 The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have focused on the resin in the silicone layer of the laminate, and have completed the present invention.
　すなわち、本発明は下記＜１＞～＜９＞に関するものである。
＜１＞シリコーン層、及びプライマー層を有する積層体であって、
　前記シリコーン層は、オイル成分、及び付加型シリコーン樹脂を含有し、
　前記オイル成分は、温度が所定値以下に低下したとき前記シリコーン層から滲出することができ、
　前記プライマー層は、前記付加型シリコーン樹脂と結合しているベースポリマーを含有する、積層体。
＜２＞前記シリコーン層は、硬化触媒を含有する、＜１＞に記載の積層体。
＜３＞前記ベースポリマーは、ヒドロシリル基含有硬化剤由来の構造単位を介して前記付加型シリコーン樹脂と結合している、＜１＞又は＜２＞に記載の積層体。
＜４＞前記プライマー層を形成するプライマー組成物は、硬化触媒を含有する、＜１＞～＜３＞のいずれか１つに記載の積層体。
＜５＞前記プライマー層を形成するプライマー組成物は、ヒドロシリル基含有硬化剤を含有する、＜１＞～＜４＞のいずれか１つに記載の積層体。
＜６＞前記ベースポリマーのＳＰ値は、７．５～１１．０（ｃａｌ／ｃｍ３）１／２である、＜１＞～＜５＞のいずれか１つに記載の積層体。
＜７＞さらに基材を有する、＜１＞～＜６＞のいずれか１つに記載の積層体。
＜８＞ＳＰ値が７．５～１１．０（ｃａｌ／ｃｍ３）１／２であるベースポリマーを含有し、
　ヒドロシリル基含有硬化剤及び硬化触媒からなる群から選択される少なくとも１種を含有する、プライマー組成物。
＜９＞ヒドロシリル基含有硬化剤と反応できる官能基を有する、＜８＞に記載のプライマー組成物。 That is, the present invention relates to the following <1> to <9>.
<1> A laminate having a silicone layer and a primer layer,
The silicone layer contains an oil component and an addition-type silicone resin,
The oil component can exude from the silicone layer when the temperature drops below a predetermined value,
The laminate, wherein the primer layer contains a base polymer bonded to the addition-type silicone resin.
<2> The laminate according to <1>, wherein the silicone layer contains a curing catalyst.
<3> The laminate according to <1> or <2>, wherein the base polymer is bonded to the addition-type silicone resin via a structural unit derived from a hydrosilyl group-containing curing agent.
<4> The laminate according to any one of <1> to <3>, wherein the primer composition forming the primer layer contains a curing catalyst.
<5> The laminate according to any one of <1> to <4>, wherein the primer composition forming the primer layer contains a hydrosilyl group-containing curing agent.
<6> The laminate according to any one of <1> to <5>, wherein the base polymer has an SP value of 7.5 to 11.0 (cal/cm 3 ) 1/2 .
<7> The laminate according to any one of <1> to <6>, further comprising a substrate.
<8> Containing a base polymer having an SP value of 7.5 to 11.0 (cal/cm 3 ) 1/2 ,
A primer composition containing at least one selected from the group consisting of a hydrosilyl group-containing curing agent and a curing catalyst.
<9> The primer composition according to <8>, which has a functional group capable of reacting with the hydrosilyl group-containing curing agent.
　本発明の積層体は、各層間の密着性に優れ、かつ優れた着氷及び／又は着雪防止機能を有する。 The laminate of the present invention has excellent adhesion between layers and has excellent anti-icing and/or anti-snowing properties.
図１は、本発明の積層体を含む層構成の一例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of a layer structure including the laminate of the present invention.
　以下、本発明の実施形態をさらに詳しく説明するが、本発明は下記実施形態に何ら制限されるものではない。 Although the embodiments of the present invention will be described in more detail below, the present invention is not limited to the following embodiments.
［積層体］
　本発明の積層体は、シリコーン層、及びプライマー層を有する。 [Laminate]
The laminate of the present invention has a silicone layer and a primer layer.
＜シリコーン層＞
　シリコーン層は、オイル成分、及び付加型シリコーン樹脂を含有する。 <Silicone layer>
The silicone layer contains an oil component and an addition-type silicone resin.
（オイル成分）
　オイル成分は、温度が所定値以下に低下したとき前記シリコーン層から滲出することができる。
　なお、上記所定値以下とは、例えば、氷点（０℃）以下を意味する。 (Oil component)
The oil component can exude from the silicone layer when the temperature drops below a predetermined value.
It should be noted that the predetermined value or lower means, for example, the freezing point (0° C.) or lower.
　オイル成分として、例えば、シリコーンオイル、炭化水素系オイル、フッ素オイル、ポリエーテル系オイル、エステル系オイル、リン化合物系オイル、鉱油系オイル、アルコール等を用いることができる。 As the oil component, for example, silicone oil, hydrocarbon oil, fluorine oil, polyether oil, ester oil, phosphorus compound oil, mineral oil, alcohol, etc. can be used.
　シリコーンオイルとしては、例えば、信越化学工業株式会社製のシリコーンオイル（例えば、ＫＦ９６Ｌシリーズ、ＫＦ９６シリーズ、ＫＦ６９シリーズ、ＫＦ９９シリーズ、ＫＦ５０シリーズ、ＫＦ５４シリーズ、ＫＦ４１０シリーズ、ＫＦ４１２シリーズ、ＫＦ４１４シリーズ、ＦＬシリーズ、ＫＦ－５６Ａ、ＫＦ－６０００、ＫＦ－６００１、ＫＦ－６００２、ＫＦ－６００３等）、モメンティブ株式会社製のシリコーンオイル（例えば、Ｅｌｅｍｅｎｔ１４＊ＰＤＭＳシリーズ、ＴＳＦ４０４シリーズ、ＴＳＦ４１０シリーズ、ＴＳＦ４３００シリーズ、ＴＳＦ４３１シリーズ、ＴＳＦ４３３シリーズ、ＴＳＦ４３７シリーズ、ＴＳＦ４４２０シリーズ、ＴＳＦ４４２１シリーズ等）、東レダウコーニング株式会社製のシリコーンオイル（例えば、ＢＹ１６－８４６シリーズ、ＳＦ８４１６シリーズ、ＳＦ８４２７シリーズ、ＳＦ－８４２８シリーズ、ＳＨ２００シリーズ、ＳＨ２０３シリーズ、ＳＨ２３０シリーズ、ＳＦ８４１９シリーズ、ＦＳ１２６５シリーズ、ＳＨ５１０シリーズ、ＳＨ５５０シリーズ、ＳＨ７１０シリーズ、ＦＺ－２１１０シリーズ、ＦＺ－２２０３シリーズ、ＢＹ１６－２０１等）、旭化成ワッカーシリコーン社製のシリコーンオイル（ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ　ＦＬＵＩＤ　ＡＫシリーズ、ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ　ＦＬＵＩＤ　ＡＰシリーズ、ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ　ＦＬＵＩＤ　ＡＲシリーズ、ＷＡＣＫＥＲ（登録商標）ＳＩＬＩＣＯＮＥ　ＦＬＵＩＤ　ＡＳシリーズ、ＷＡＣＫＥＲ（登録商標）ＴＮシリーズ、ＷＡＣＫＥＲ（登録商標）Ｌシリーズ、ＷＡＣＫＥＲ（登録商標）ＡＦシリーズ等）等を用いることができる。
　炭化水素系オイルとしては流動パラフィン等を用いることができる。 Examples of silicone oils include silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. (e.g., KF96L series, KF96 series, KF69 series, KF99 series, KF50 series, KF54 series, KF410 series, KF412 series, KF414 series, FL series, KF -56A, KF-6000, KF-6001, KF-6002, KF-6003, etc.), silicone oil manufactured by Momentive Co., Ltd. (for example, Element 14 * PDMS series, TSF404 series, TSF410 series, TSF4300 series, TSF431 series, TSF433 series , TSF437 series, TSF4420 series, TSF4421 series, etc.), Silicone oil manufactured by Dow Corning Toray Co., Ltd. series, FS1265 series, SH510 series, SH550 series, SH710 series, FZ-2110 series, FZ-2203 series, BY16-201, etc.), silicone oil manufactured by Asahi Kasei Wacker Silicone Co., Ltd. (WACKER (registered trademark) SILICONE FLUID AK series, WACKER (registered trademark) SILICONE FLUID AP series, WACKER (registered trademark) SILICONE FLUID AR series, WACKER (registered trademark) SILICONE FLUID AS series, WACKER (registered trademark) TN series, WACKER (registered trademark) L series, WACKER (registered trademark) AF series, etc.) can be used.
Liquid paraffin or the like can be used as the hydrocarbon oil.
（付加型シリコーン樹脂）
　シリコーン層は、付加型シリコーン樹脂を含有する。シリコーン層が付加型シリコーン樹脂を含有することにより、付加型シリコーン樹脂とプライマー層中のベースポリマーが結合し、シリコーン層とプライマー層の密着性が向上する。 (addition type silicone resin)
The silicone layer contains an addition-type silicone resin. By containing the addition-type silicone resin in the silicone layer, the addition-type silicone resin and the base polymer in the primer layer are bonded, and the adhesion between the silicone layer and the primer layer is improved.
　本発明において、付加型シリコーン樹脂とは、不飽和基（炭素－炭素二重結合）を有するシリコーン樹脂が硬化剤によって硬化することにより得られる、付加反応で重合した樹脂を意味する。 In the present invention, the addition-type silicone resin means a resin polymerized by an addition reaction obtained by curing a silicone resin having an unsaturated group (carbon-carbon double bond) with a curing agent.
　不飽和基（炭素－炭素二重結合）を有するシリコーン樹脂における不飽和基としては、例えば、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ヘキセニル基等が挙げられる。これらの中でも、シリコーン層とプライマー層の密着性向上の観点から、ビニル基が好ましい。 Examples of unsaturated groups in silicone resins having unsaturated groups (carbon-carbon double bonds) include vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, and hexenyl groups. Among these, a vinyl group is preferable from the viewpoint of improving the adhesion between the silicone layer and the primer layer.
　不飽和基（炭素－炭素二重結合）を有するシリコーン樹脂は、例えば主鎖がジオルガノシロキサンの繰返し単位であり、末端がトリオルガノシロキサン構造であるものが例示され、分岐や環状構造を有するものであってもよい。末端や繰返し単位中のケイ素に結合するオルガノ基としては、メチル基、エチル基、フェニル基等が例示される。具体例としては、両末端にビニル基を有するメチルポリシロキサン等が挙げられる。 Examples of silicone resins having unsaturated groups (carbon-carbon double bonds) include those whose main chain is a repeating unit of diorganosiloxane and whose terminal is a triorganosiloxane structure, and those having a branched or cyclic structure. may be Examples of the organo groups bonded to silicon in terminals and repeating units include methyl, ethyl, and phenyl groups. Specific examples include methylpolysiloxane having vinyl groups at both ends.
　具体的な不飽和基（炭素－炭素二重結合）を有するシリコーン樹脂としては、例えば、信越化学工業株式会社製のＫＥ－１３１０ＳＴ、ＫＥ－１９３５Ａ／ＫＥ－１９３５Ｂ、ＫＥ－１９５０Ａ／ＫＥ－１９５０Ｂ、ＫＥ－１０３、ＫＥ－１３１６、ＫＥ－１６００、ＫＥ－１６０６、ＫＥ－１２０４Ａ／ＫＥ－１２０４Ｂ等が挙げられる。 Examples of silicone resins having specific unsaturated groups (carbon-carbon double bonds) include KE-1310ST, KE-1935A/KE-1935B, KE-1950A/KE-1950B manufactured by Shin-Etsu Chemical Co., Ltd., KE-103, KE-1316, KE-1600, KE-1606, KE-1204A/KE-1204B and the like.
　硬化剤は、ヒドロシリル基（ＳｉＨ基）を含有することが好ましく、末端及び／又は繰返し構造中において、２個以上のヒドロシリル基を含有することがより好ましい。硬化剤は、例えば主鎖がジオルガノシロキサンの繰返し単位であり、末端がトリオルガノシロキサン構造であるものが例示され、分岐や環状構造を有するものであってもよい。末端や繰返し単位中のケイ素に結合するオルガノ基としては、メチル基、エチル基、オクチル基、フェニル基などが例示され、これらの２個以上が水素に置換された硬化剤が好ましい。具体例としては、ハイドロジェンシリコーン等が挙げられる。 The curing agent preferably contains hydrosilyl groups (SiH groups), and more preferably contains two or more hydrosilyl groups at the terminals and/or in the repeating structure. The curing agent is exemplified by a repeating unit of diorganosiloxane as a main chain and a triorganosiloxane structure as a terminal, and may have a branched or cyclic structure. Silicon-bonded organo groups in terminals and repeating units are exemplified by methyl, ethyl, octyl, and phenyl groups, and curing agents in which two or more of these groups are substituted with hydrogen are preferred. Specific examples include hydrogen silicone and the like.
　具体的な硬化剤としては、例えば、信越化学工業株式会社製のｃａｔ－１３１０ｓ、ＫＦ－９９、ＫＦ－９９０１、Ｇｅｌｅｓｔ社製のＨＭＳ－１５１、ＨＭＳ－３０１、ＨＭＳ－５０１等が挙げられる。 Examples of specific curing agents include cat-1310s, KF-99, and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., HMS-151, HMS-301, and HMS-501 manufactured by Gelest.
　また、不飽和基（炭素－炭素二重結合）を有するシリコーン樹脂と硬化剤の反応は、硬化触媒の存在下で行われることが好ましい。すなわち、シリコーン層は、硬化触媒を含有することが好ましい。 Also, the reaction between the silicone resin having an unsaturated group (carbon-carbon double bond) and the curing agent is preferably carried out in the presence of a curing catalyst. That is, the silicone layer preferably contains a curing catalyst.
　硬化触媒としては、例えば、白金触媒等が挙げられる。 Examples of curing catalysts include platinum catalysts.
＜プライマー層＞
　プライマー層は、ベースポリマーを含有し、当該ベースポリマーはシリコーン層中の付加型シリコーン樹脂と結合し、その結果、シリコーン層とプライマー層の密着性が向上する。 <Primer layer>
The primer layer contains a base polymer that bonds with the addition-type silicone resin in the silicone layer, resulting in improved adhesion between the silicone layer and the primer layer.
（ベースポリマー）
　ベースポリマーのＳＰ値は、７．５～１１．０（ｃａｌ／ｃｍ３）１／２であることが好ましい。ベースポリマーのＳＰ値が上記範囲内であると、シリコーン層中のオイル成分がプライマー層へ移行することを防ぐことができ、プライマー層の膨潤による強度低下を防ぐことができる。 (base polymer)
The SP value of the base polymer is preferably 7.5 to 11.0 (cal/cm 3 ) 1/2 . When the SP value of the base polymer is within the above range, it is possible to prevent the oil component in the silicone layer from migrating to the primer layer, thereby preventing a decrease in strength due to swelling of the primer layer.
　ベースポリマーのＳＰ値は、オイル成分の移行を防ぐ観点から、７．６～１０．９（ｃａｌ／ｃｍ３）１／２がより好ましく、７．８～１０．７（ｃａｌ／ｃｍ３）１／２がさらに好ましく、８．０～１０．５（ｃａｌ／ｃｍ３）１／２が特に好ましい。
　なお、ＳＰ値は実施例に記載の方法で測定することができる。 The SP value of the base polymer is more preferably 7.6 to 10.9 (cal/cm 3 ) 1/2 , more preferably 7.8 to 10.7 (cal/cm 3 ) 1 from the viewpoint of preventing migration of oil components. /2 is more preferable, and 8.0 to 10.5 (cal/cm 3 ) 1/2 is particularly preferable.
The SP value can be measured by the method described in Examples.
　また、シリコーン層とプライマー層の密着性をより向上させる観点から、付加型シリコーン樹脂の硬化反応に用いる硬化剤はヒドロシリル基含有硬化剤であることが好ましく、プライマー層中のベースポリマーは、当該ヒドロシリル基含有硬化剤由来の構造単位を介して付加型シリコーン樹脂と結合していることが好ましい。 Further, from the viewpoint of further improving the adhesion between the silicone layer and the primer layer, the curing agent used in the curing reaction of the addition-type silicone resin is preferably a hydrosilyl group-containing curing agent, and the base polymer in the primer layer is the hydrosilyl It is preferably bonded to the addition-type silicone resin via a structural unit derived from the group-containing curing agent.
　ベースポリマーとしては、例えば、アクリルゴム、ジエン系ゴムなどの熱硬化性エラストマー、ＳＢＳ（スチレン－ブタジエン－スチレンブロック共重合体）、ＳＩＳ（スチレン－イソプレン－スチレンブロック共重合体）、ＳＥＰＳ（スチレン－エチレン・プロピレン－スチレンブロック共重合体）、ＳＢＲ（スチレンブタジエンゴム）、ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体）などのスチレン系熱可塑性エラストマー、ポリメタクリル酸メチルとアクリル酸アルキルエステルとのブロック共重合体（アクリル系熱可塑性エラストマー）、ＥＰＤＭ（エチレンプロピレンジエンゴム）、ＥＰＴ（エチレンプロピレンゴム）、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）等が挙げられる。これらの中でも、シリコーン層とプライマー層の密着性向上の観点から、ＳＥＢＳが好ましい。 Examples of base polymers include thermosetting elastomers such as acrylic rubber and diene rubber, SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), SEPS (styrene- ethylene-propylene-styrene block copolymer), SBR (styrene-butadiene rubber), SEBS (styrene-ethylene-butylene-styrene block copolymer) and other styrene thermoplastic elastomers, polymethyl methacrylate and acrylic acid alkyl ester block copolymer (thermoplastic acrylic elastomer), EPDM (ethylene propylene diene rubber), EPT (ethylene propylene rubber), PE (polyethylene), PP (polypropylene), and the like. Among these, SEBS is preferable from the viewpoint of improving the adhesion between the silicone layer and the primer layer.
　さらに、ベースポリマーは、官能基を有することが好ましい。ベースポリマーが官能基を有することによって、官能基とシリコーン層中の付加型シリコーン樹脂とが結合し、シリコーン層とプライマー層の密着性が向上する。 Furthermore, the base polymer preferably has a functional group. When the base polymer has a functional group, the functional group bonds with the addition-type silicone resin in the silicone layer, improving the adhesion between the silicone layer and the primer layer.
　当該官能基としては、例えば、直鎖状、分枝状、又は環状のアルケニル基（イソプロペニル基、ビニル基、１－プロペニル基、１－ブテニル基、１－メチル－１－プロペニル基、１－シクロペンテニル基、１－シクロヘキセニル基等）、アミノ基、カルボキシル基、水酸基、エポキシ基、シラノール基、マレイン酸基等が挙げられる。これらの中でも、シリコーン層とプライマー層の密着性向上の観点から、ビニル基、イソプロペニル基が好ましく、イソプロペニル基がより好ましい。 Examples of the functional group include linear, branched, or cyclic alkenyl groups (isopropenyl group, vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1- cyclopentenyl group, 1-cyclohexenyl group, etc.), amino group, carboxyl group, hydroxyl group, epoxy group, silanol group, maleic acid group and the like. Among these, a vinyl group and an isopropenyl group are preferable, and an isopropenyl group is more preferable, from the viewpoint of improving the adhesion between the silicone layer and the primer layer.
（プライマー組成物）
　プライマー層は、プライマー組成物から形成される。
　プライマー組成物は、上述のベースポリマーの他に、上述の硬化触媒を含有することが好ましい。プライマー組成物が硬化触媒を含有すると、プライマー組成物が有する官能基がシリコーン層の官能基と反応しやすくなるので、シリコーン層とプライマー層の密着性が向上する。 (Primer composition)
A primer layer is formed from a primer composition.
The primer composition preferably contains the curing catalyst described above in addition to the base polymer described above. When the primer composition contains a curing catalyst, the functional groups of the primer composition are more likely to react with the functional groups of the silicone layer, thereby improving the adhesion between the silicone layer and the primer layer.
　また、プライマー組成物は、上述のベースポリマーの他に、上述のヒドロシリル基含有硬化剤を含有することが好ましい。プライマー組成物がヒドロシリル基含有硬化剤を含有すると、プライマー層がヒドロシリル基含有硬化剤由来の構造単位を介してシリコーン層中の付加型シリコーン樹脂と結合し、シリコーン層とプライマー層の密着性が向上する。 In addition, the primer composition preferably contains the above-mentioned hydrosilyl group-containing curing agent in addition to the above-mentioned base polymer. When the primer composition contains a hydrosilyl group-containing curing agent, the primer layer bonds with the addition-type silicone resin in the silicone layer via structural units derived from the hydrosilyl group-containing curing agent, and the adhesion between the silicone layer and the primer layer is improved. do.
　また、プライマー組成物は、上述のベースポリマーの他に、さらに、シリコーン層中の付加型シリコーン樹脂と結合しないブレンドポリマーを含有することができる。ブレンドポリマーが含まれると、基材とプライマー層の密着性が向上する。 In addition to the base polymer described above, the primer composition may further contain a blend polymer that does not bond with the addition-type silicone resin in the silicone layer. The inclusion of the blend polymer improves the adhesion between the substrate and the primer layer.
　ブレンドポリマーとしては、例えば、アクリルゴム、ジエン系ゴムなどの熱硬化性エラストマー、ＳＢＳ（スチレン－ブタジエン－スチレンブロック共重合体）、ＳＩＳ（スチレン－イソプレン－スチレンブロック共重合体）、ＳＥＰＳ（スチレン－エチレン・プロピレン－スチレンブロック共重合体）、ＳＢＲ（スチレンブタジエンゴム）、ＳＥＢＳ（スチレン－エチレン・ブチレン－スチレンブロック共重合体）などのスチレン系熱可塑性エラストマー、ポリメタクリル酸メチルとアクリル酸アルキルエステルとのブロック共重合体（アクリル系熱可塑性エラストマー）、ＥＰＤＭ（エチレンプロピレンジエンゴム）、ＥＰＴ（エチレンプロピレンゴム）、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）等が挙げられる。これらの中でも、基材とプライマー層の密着性向上の観点から、ＳＥＢＳが好ましい。 Examples of blend polymers include thermosetting elastomers such as acrylic rubber and diene rubber, SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene block copolymer), SEPS (styrene- ethylene-propylene-styrene block copolymer), SBR (styrene-butadiene rubber), SEBS (styrene-ethylene-butylene-styrene block copolymer) and other styrene thermoplastic elastomers, polymethyl methacrylate and acrylic acid alkyl ester block copolymer (thermoplastic acrylic elastomer), EPDM (ethylene propylene diene rubber), EPT (ethylene propylene rubber), PE (polyethylene), PP (polypropylene), and the like. Among these, SEBS is preferable from the viewpoint of improving the adhesion between the substrate and the primer layer.
　さらに、ブレンドポリマーは、官能基を有することが好ましい。ブレンドポリマーが官能基を有することによって、官能基と基材との相互作用が強まり、基材とプライマー層の密着性が向上する。 Furthermore, the blend polymer preferably has a functional group. By having a functional group in the blend polymer, the interaction between the functional group and the base material is strengthened, and the adhesion between the base material and the primer layer is improved.
　当該官能基としては、例えば、直鎖状、分枝状、又は環状のアルケニル基（イソプロペニル基、ビニル基、１－プロペニル基、１－ブテニル基、１－メチル－１－プロペニル基、１－シクロペンテニル基、１－シクロヘキセニル基等）、アミノ基、カルボキシル基、水酸基、エポキシ基、シラノール基、マレイン酸基等が挙げられる。これらの中でも、基材とプライマー層の密着性向上の観点から、マレイン酸基、アミノ基が好ましい。 Examples of the functional group include linear, branched, or cyclic alkenyl groups (isopropenyl group, vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1- cyclopentenyl group, 1-cyclohexenyl group, etc.), amino group, carboxyl group, hydroxyl group, epoxy group, silanol group, maleic acid group and the like. Among these, a maleic acid group and an amino group are preferable from the viewpoint of improving the adhesion between the substrate and the primer layer.
＜積層体の製造方法＞
　本発明の積層体は、例えば図１に示すように、基材１３の上にプライマー層１１を形成し、その上にシリコーン層１２を形成することによって得ることができる。 <Method for manufacturing laminate>
The laminate of the present invention can be obtained, for example, by forming a primer layer 11 on a substrate 13 and forming a silicone layer 12 thereon, as shown in FIG.
　具体的には、例えば、プライマー層を形成するプライマー組成物を、ハケ塗り、スプレー塗装、各種コーター塗装などの一般的な方法で基材に塗装する。塗装は、通常１～２回行われる。なお、プライマー層を形成するプライマー組成物は、各成分を、公知の方法によって混合及び／又は撹拌して得ることができる。 Specifically, for example, the primer composition that forms the primer layer is applied to the base material by general methods such as brushing, spray coating, and various coater coatings. Coating is usually carried out 1-2 times. The primer composition for forming the primer layer can be obtained by mixing and/or stirring each component by a known method.
　プライマー層の厚みは、特に限定されないが、１０～５００μｍが好ましく、３０～２００μｍがより好ましい。 Although the thickness of the primer layer is not particularly limited, it is preferably 10-500 μm, more preferably 30-200 μm.
　なお、基材としては、例えば、ポリウレタン樹脂、ポリウレタンアクリル樹脂、ゴム系樹脂、塩化ビニル樹脂、ポリエステル樹脂、シリコーン樹脂、エラストマー類、フッ素樹脂、ポリアミド樹脂、ポリオレフィン樹脂（ポリエチレン、ポリプロピレン、ＡＢＳ、ＡＥＳ、ＡＳ、アイオノマー等）また、金属板若しくは金属箔（アルミニウム、銅、銀、鉄、ニッケル、スズ、ステンレス等）、コンクリート、セラミックス等を用いることができる。 Examples of base materials include polyurethane resins, polyurethane acrylic resins, rubber resins, vinyl chloride resins, polyester resins, silicone resins, elastomers, fluororesins, polyamide resins, polyolefin resins (polyethylene, polypropylene, ABS, AES, AS, ionomer, etc.), metal plates or foils (aluminum, copper, silver, iron, nickel, tin, stainless steel, etc.), concrete, ceramics, etc. can also be used.
　プライマー層を形成するプライマー組成物を、基材に塗装した後は、例えば－１０～１８０℃の環境下で、例えば３分～３時間静置することによってプライマー組成物を硬化又は乾燥させることができる。 After coating the substrate with the primer composition that forms the primer layer, the primer composition can be cured or dried by standing for 3 minutes to 3 hours, for example, in an environment of -10 to 180°C. can.
　次に、プライマー層の上に、シリコーン層を形成するシリコーン組成物を、ハケ塗り、スプレー塗装、各種コーター塗装などの一般的な方法でプライマー層に塗装する。塗装は、通常１～２回行われる。なお、シリコーン層を形成するシリコーン組成物は、各成分を、公知の方法によって混合及び／又は撹拌して得ることができる。 Next, on the primer layer, a silicone composition that forms a silicone layer is applied to the primer layer by a general method such as brush coating, spray coating, and various coater coatings. Coating is usually carried out 1-2 times. The silicone composition forming the silicone layer can be obtained by mixing and/or stirring each component by a known method.
　シリコーン層の厚みは、特に限定されないが、オイル成分がシリコーン層の表面まで容易に透過することができるように、言い換えれば、シリコーン層に対するオイル透過性を担保するため、５００μｍ以下が好ましく、また、強度の点から、５０μｍ以上が好ましい。 The thickness of the silicone layer is not particularly limited, but is preferably 500 μm or less so that the oil component can easily permeate to the surface of the silicone layer, in other words, to ensure oil permeability to the silicone layer. From the viewpoint of strength, the thickness is preferably 50 μm or more.
　シリコーン層を形成するシリコーン組成物を、プライマー層に塗装した後は、例えば－１０～１８０℃の環境下で、例えば３分～７日静置することによってシリコーン組成物を硬化又は乾燥させ、積層体を得ることができる。 After coating the primer layer with the silicone composition that forms the silicone layer, the silicone composition is cured or dried by allowing it to stand in an environment of, for example, −10 to 180° C. for, for example, 3 minutes to 7 days, followed by lamination. you can get a body
　なお、プライマー層を形成するプライマー組成物の硬化又は乾燥とシリコーン層を形成するシリコーン組成物の硬化又は乾燥は、同時に行ってもよいし、別々に行ってもよい。 The curing or drying of the primer composition forming the primer layer and the curing or drying of the silicone composition forming the silicone layer may be carried out simultaneously or separately.
　また、プライマー層を形成するプライマー組成物及びシリコーン層を形成するシリコーン組成物は、上述の成分の他に、シリカなどの無機フィラーを含有することができる。
　シリカとしては、例えば、日本アエロジル株式会社製のシリカ（例えば、ＡＥＲＯＳＩＬ５０、１３０、２００、３００、Ｒ９７２、Ｒ９７４、Ｒ９７６、ＲＸ５０、ＲＸ２００、ＲＸ３００、ＲＹ５０、ＲＹ３００、Ｒ７２００、Ｒ８２００、Ｒ９２００）等を用いることができる。 In addition to the components described above, the primer composition forming the primer layer and the silicone composition forming the silicone layer may contain an inorganic filler such as silica.
As the silica, for example, silica manufactured by Nippon Aerosil Co., Ltd. (e.g., AEROSIL50, 130, 200, 300, R972, R974, R976, RX50, RX200, RX300, RY50, RY300, R7200, R8200, R9200) and the like can be used. can be done.
　シリコーン層におけるオイル成分の含有量は、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上に設定することができる。また、オイル成分の含有量は、好ましくは８５質量％以下、より好ましくは８０質量％以下、さらに好ましくは７５質量％以下に設定することができる。 The content of the oil component in the silicone layer can be set to preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Also, the content of the oil component can be set to preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
　シリコーン層における付加型シリコーン樹脂の含有量は、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上に設定することができる。また、付加型シリコーン樹脂の含有量は、好ましくは８５質量％以下、より好ましくは８０質量％以下、さらに好ましくは７５質量％以下に設定することができる。 The content of the addition-type silicone resin in the silicone layer can be set to preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. Also, the content of the addition-type silicone resin can be set to preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.
　シリコーン層における硬化触媒の含有量は、好ましくは０．００００１質量％以上、より好ましくは０．０００１質量％以上、さらに好ましくは０．０００５質量％以上に設定することができる。また、硬化触媒の含有量は、好ましくは５質量％以下、より好ましくは４質量％以下、さらに好ましくは３質量％以下に設定することができる。 The content of the curing catalyst in the silicone layer can be set to preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.0005% by mass or more. Also, the content of the curing catalyst can be set to preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
　プライマー層におけるベースポリマーの含有量は、好ましくは３０質量％以上、より好ましくは４０質量％以上、さらに好ましくは５０質量％以上に設定することができる。また、ベースポリマーの含有量は、好ましくは１００質量％以下、より好ましくは９９．９９質量％以下、さらに好ましくは９９．９８質量％以下に設定することができる。 The content of the base polymer in the primer layer can be set to preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Also, the content of the base polymer can be set to preferably 100% by mass or less, more preferably 99.99% by mass or less, and even more preferably 99.98% by mass or less.
　プライマー層における硬化触媒の含有量は、好ましくは０．００００１質量％以上、より好ましくは０．０００１質量％以上、さらに好ましくは０．０００５質量％以上に設定することができる。また、硬化触媒の含有量は、好ましくは５質量％以下、より好ましくは４質量％以下、さらに好ましくは３質量％以下に設定することができる。 The content of the curing catalyst in the primer layer can be set to preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.0005% by mass or more. Also, the content of the curing catalyst can be set to preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
　プライマー層におけるヒドロシリル基含有硬化剤の含有量は、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上、さらに好ましくは０．０２質量％以上に設定することができる。また、ヒドロシリル基含有硬化剤の含有量は、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下に設定することができる。 The content of the hydrosilyl group-containing curing agent in the primer layer can be set to preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more. Also, the content of the hydrosilyl group-containing curing agent can be set to preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
　プライマー層におけるブレンドポリマーの含有量は、好ましくは１質量％以上、より好ましくは３質量％以上、さらに好ましくは５質量％以上に設定することができる。また、ブレンドポリマーの含有量は、好ましくは９０質量％以下、より好ましくは８０質量％以下、さらに好ましくは７０質量％以下に設定することができる。 The content of the blend polymer in the primer layer can be set to preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. Also, the content of the blend polymer can be set to preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
　以下に実施例を挙げ、本発明を具体的に説明するが、本発明は何らこれらに限定されるものではない。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
＜積層体の作製＞
［実施例１］
（プライマー層）
　プライマー層成分として、ベースポリマー：ハイブラー５１２７（株式会社クラレ製）、硬化（架橋）剤：ハイドロジェンシロキサンオイル（信越化学工業株式会社製、品番：ＫＦ－９９０１）、硬化触媒（信越化学工業株式会社製、品番：ＣＡＴ－ＰＬ－５０Ｔ）を用意した。 <Production of laminate>
[Example 1]
(primer layer)
As primer layer components, base polymer: Hybler 5127 (manufactured by Kuraray Co., Ltd.), curing (crosslinking) agent: hydrogen siloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-9901), curing catalyst (Shin-Etsu Chemical Co., Ltd. product, product number: CAT-PL-50T).
　ベースポリマーをトルエンに溶解させ、ベースポリマーの含有量が２０質量％のトルエン溶液を作製した。当該トルエン溶液（９９．２質量％）、ハイドロジェンシロキサンオイル（０．６質量％）、硬化触媒（０．２質量％）を２５℃、１０１ｋＰａの条件下で混合した。得られた混合液をスパチュラで約１２０ｒｐｍの速さで６０秒間撹拌し、プライマー組成物を得た。 A base polymer was dissolved in toluene to prepare a toluene solution with a base polymer content of 20% by mass. The toluene solution (99.2% by mass), hydrogensiloxane oil (0.6% by mass), and curing catalyst (0.2% by mass) were mixed under conditions of 25° C. and 101 kPa. The resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a primer composition.
　プライマー組成物を、ＰＥＴ（ポリエチレンテレフタラート）フィルム（東レ株式会社製、ルミラー（登録商標）７５－Ｓ１０）にベーカーアプリケーター(ヨシミツ精機株式会社製　ＹＢＡ型５型)を用いて２００μｍ厚で塗装し、２５℃環境下において３０分乾燥（トルエンを揮発）、させることによってプライマー層を形成した。 The primer composition is applied to a PET (polyethylene terephthalate) film (Lumirror (registered trademark) 75-S10 manufactured by Toray Industries, Inc.) using a baker applicator (YBA type 5 manufactured by Yoshimitsu Seiki Co., Ltd.) to a thickness of 200 μm, A primer layer was formed by drying (evaporating toluene) in an environment of 25° C. for 30 minutes.
（シリコーン層及び積層体）
　シリコーン層成分として、樹脂成分(常温硬化型)：ＫＥ－１３１０ＳＴ（信越化学工業株式会社製、ビニル基を有するシリコーン樹脂、シリカ含有）、硬化剤（信越化学工業株式会社製、品番：ｃaｔ－１３１０ｓ、ハイドロジェンシリコーン、白金触媒含有）、第１オイル成分（相溶オイル）：ジメチルシロキサンオイル（信越化学工業株式会社製、品番：ＫＦ－９６（５０ｃｓ））、第２オイル成分（非相溶オイル）：カルビノールオイル（信越化学工業株式会社製、品番：ＫＦ－６００２）、硬化触媒（信越化学工業株式会社製、品番：ＣＡＴ－ＰＬ－５０Ｔ）を用意した。 (Silicone layer and laminate)
As silicone layer components, resin component (room temperature curing type): KE-1310ST (manufactured by Shin-Etsu Chemical Co., Ltd., silicone resin having a vinyl group, containing silica), curing agent (manufactured by Shin-Etsu Chemical Co., Ltd., product number: cat-1310s , hydrogen silicone, containing platinum catalyst), first oil component (compatible oil): dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-96 (50cs)), second oil component (incompatible oil ): Carbinol oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6002) and a curing catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., product number: CAT-PL-50T) were prepared.
　樹脂成分（４７．４質量％）、第１オイル成分（２１．３質量％）、第２オイル成分（２６．１質量％）を、２５℃、１０１ｋＰａの条件下で混合した。得られた混合液をスパチュラで約１２０ｒｐｍの速さで６０秒間撹拌し、ディスパー（プライミクス株式会社製、ラボ・リューション）で２０００ｒｐｍの速さで５分間撹拌した。硬化剤（４．７質量％）および硬化触媒（０．５質量％）を加えて、スパチュラで約１２０ｒｐｍの速さで６０秒間撹拌し、シリコーン組成物を得た。 A resin component (47.4% by mass), a first oil component (21.3% by mass), and a second oil component (26.1% by mass) were mixed under conditions of 25°C and 101 kPa. The resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds, and then stirred with a Disper (Labo Solution, manufactured by Primix Co., Ltd.) at a speed of 2000 rpm for 5 minutes. A curing agent (4.7% by mass) and a curing catalyst (0.5% by mass) were added and stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a silicone composition.
　シリコーン組成物を、上述のプライマー層上にベーカーアプリケーター(ヨシミツ精機株式会社製　ＹＢＡ型５型)を用いて５００μｍ厚で塗装し、２５℃環境下において１週間、硬化させることによって積層体を形成した。 The silicone composition was applied on the above-described primer layer with a baker applicator (YBA type 5 manufactured by Yoshimitsu Seiki Co., Ltd.) to a thickness of 500 μm, and cured in an environment of 25° C. for 1 week to form a laminate. .
［実施例２］
（プライマー層）
　ハイドロジェンシロキサンオイル、硬化触媒を用いなかったこと以外は、実施例１と同様の操作をし、プライマー層を形成した。 [Example 2]
(primer layer)
A primer layer was formed in the same manner as in Example 1 except that hydrogensiloxane oil and curing catalyst were not used.
（シリコーン層及び積層体）
　実施例１で用いた成分の他に、第２オイル成分としてフェニルオイル（モメンティブ社製、品番：ＴＳＦ－４３７）を用意し、さらに追加で硬化（架橋）剤としてハイドロジェンシロキサンオイル（信越化学工業株式会社製、品番：ＫＦ－９９０１）を用意した。 (Silicone layer and laminate)
In addition to the components used in Example 1, phenyl oil (manufactured by Momentive, product number: TSF-437) was prepared as a second oil component, and hydrogensiloxane oil (Shin-Etsu Chemical Co., Ltd.) was additionally used as a curing (crosslinking) agent. Co., Ltd., product number: KF-9901) was prepared.
　樹脂成分（４６．７質量％）、第１オイル成分（２０．６質量％）、第２オイル成分（２６．１質量％）、硬化（架橋）剤（１．４質量％）を、２５℃、１０１ｋＰａの条件下で混合した。得られた混合液をスパチュラで約１２０ｒｐｍの速さで６０秒間撹拌し、ディスパー（プライミクス株式会社製、ラボ・リューション）で２０００ｒｐｍの速さで５分間撹拌した。硬化剤（４．７質量％）および硬化触媒（０．５質量％）を加えて、スパチュラで約１２０ｒｐｍの速さで６０秒間撹拌し、シリコーン組成物を得た。 A resin component (46.7% by mass), a first oil component (20.6% by mass), a second oil component (26.1% by mass), and a curing (crosslinking) agent (1.4% by mass) were heated at 25°C. , 101 kPa. The resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds, and then stirred with a Disper (Labo Solution, manufactured by Primix Co., Ltd.) at a speed of 2000 rpm for 5 minutes. A curing agent (4.7% by mass) and a curing catalyst (0.5% by mass) were added and stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a silicone composition.
　シリコーン組成物を、上述のプライマー層に、実施例１と同様の操作で塗装及び硬化させることによって積層体を形成した。 A laminate was formed by coating and curing the silicone composition on the primer layer described above in the same manner as in Example 1.
[実施例３]
（プライマー層）
　実施例１と同様の操作をし、プライマー層を形成した。 [Example 3]
(primer layer)
The same operation as in Example 1 was performed to form a primer layer.
（シリコーン層及び積層体）
　シリコーン組成物の成分及び含有量を表２に示したものとした以外は、実施例２と同様の操作をし、積層体を形成した。 (Silicone layer and laminate)
A laminate was formed in the same manner as in Example 2, except that the components and contents of the silicone composition were as shown in Table 2.
[実施例４]
（プライマー層）
　実施例１と同様の操作をし、プライマー層を形成した。 [Example 4]
(primer layer)
The same operation as in Example 1 was performed to form a primer layer.
（シリコーン層及び積層体）
　シリコーン層成分として、樹脂成分(加熱硬化型)：ＫＥ－１９３５Ａ/ＫＥ－１９３５Ｂ（信越化学工業株式会社製）を質量比１：１で混合したシリコーン樹脂（ビニル基を有するシリコーン樹脂、ハイドロジェンシリコーン及び白金触媒含有）、第１オイル成分（相溶オイル）：ジメチルシロキサンオイル（信越化学工業株式会社製、品番：ＫＦ－９６（５０ｃｓ））、第２オイル成分（非相溶オイル）：カルビノールオイル（信越化学工業株式会社製、品番：ＫＦ－６００２）を用意した。 (Silicone layer and laminate)
As a silicone layer component, a silicone resin (silicone resin having a vinyl group, hydrogen silicone and platinum catalyst), first oil component (compatible oil): dimethylsiloxane oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-96 (50cs)), second oil component (incompatible oil): carbinol An oil (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KF-6002) was prepared.
　各成分の含有量を表２に示したものとした以外は、実施例１と同様の操作をし、シリコーン組成物を得た。 A silicone composition was obtained in the same manner as in Example 1, except that the content of each component was as shown in Table 2.
　シリコーン組成物を、上述のプライマー層上に５００μｍ厚で塗装し、１５０℃で１０分乾燥させることで積層体を形成した。 A laminate was formed by applying the silicone composition to a thickness of 500 μm on the above primer layer and drying at 150° C. for 10 minutes.
[実施例５]
（プライマー層）
　プライマー組成物の成分及び含有量を表１に示したものとした以外は、実施例１と同様の操作をし、プライマー層を形成した。 [Example 5]
(primer layer)
A primer layer was formed in the same manner as in Example 1, except that the components and contents of the primer composition were as shown in Table 1.
（シリコーン層及び積層体）
　実施例４と同様の操作をし、シリコーン層及び積層体を形成した。 (Silicone layer and laminate)
The same operation as in Example 4 was performed to form a silicone layer and a laminate.
［実施例６］
（プライマー層）
　プライマー組成物の成分及び含有量を表１に示したものとした以外は、実施例１と同様の操作をし、プライマー層を形成した。
　なお、表１に記載の「クレイトンＦＧ１９０１ＧＴ」はクレイトンポリマー社製の無水マレイン酸変性ＳＥＢＳである。 [Example 6]
(primer layer)
A primer layer was formed in the same manner as in Example 1, except that the components and contents of the primer composition were as shown in Table 1.
"Kraton FG1901GT" shown in Table 1 is maleic anhydride-modified SEBS manufactured by Kraton Polymer.
（シリコーン層及び積層体）
　実施例１と同様の操作をし、シリコーン層及び積層体を形成した。 (Silicone layer and laminate)
The same operation as in Example 1 was performed to form a silicone layer and a laminate.
［実施例７］
（プライマー層）
　プライマー組成物の成分及び含有量を表１に示したものとした以外は、実施例１と同様の操作をし、プライマー層を形成した。
　なお、表１に記載の「タフテックＭＰ１０」は旭化成社製のアミン変性ＳＥＢＳである。 [Example 7]
(primer layer)
A primer layer was formed in the same manner as in Example 1, except that the components and contents of the primer composition were as shown in Table 1.
In addition, "Tuftech MP10" described in Table 1 is an amine-modified SEBS manufactured by Asahi Kasei Corporation.
（シリコーン層及び積層体）
　実施例１と同様の操作をし、シリコーン層及び積層体を形成した。 (Silicone layer and laminate)
The same operation as in Example 1 was performed to form a silicone layer and a laminate.
[比較例１]
（プライマー層）
　プライマー層成分として、ベースポリマー：セプトン８００７Ｌ（株式会社クラレ製）を用意した。 [Comparative Example 1]
(primer layer)
As a primer layer component, a base polymer: Septon 8007L (manufactured by Kuraray Co., Ltd.) was prepared.
　ベースポリマーをトルエンに溶解させ、ベースポリマーの含有量が２０質量％のトルエン溶液を作製した。当該トルエン溶液を２５℃、１０１ｋＰａの条件下で混合した。得られた混合液をスパチュラで約１２０ｒｐｍの速さで６０秒間撹拌し、プライマー組成物を得た。 A base polymer was dissolved in toluene to prepare a toluene solution with a base polymer content of 20% by mass. The toluene solutions were mixed under conditions of 25° C. and 101 kPa. The resulting mixture was stirred with a spatula at a speed of about 120 rpm for 60 seconds to obtain a primer composition.
　実施例１と同様の操作をし、プライマー組成物からプライマー層を形成した。 A primer layer was formed from the primer composition by performing the same operation as in Example 1.
（シリコーン層及び積層体）
　シリコーン組成物の成分及び含有量を表２に示したものとした以外は、実施例１と同様の操作をし、シリコーン組成物を得た。 (Silicone layer and laminate)
A silicone composition was obtained in the same manner as in Example 1, except that the components and contents of the silicone composition were as shown in Table 2.
[比較例２]
（プライマー層）
　比較例１と同様の操作をし、プライマー層を形成した。 [Comparative Example 2]
(primer layer)
The same operation as in Comparative Example 1 was performed to form a primer layer.
（シリコーン層及び積層体）
　シリコーン組成物の成分及び含有量を表２に示したものとした以外は、実施例１と同様の操作をし、シリコーン組成物を得た。 (Silicone layer and laminate)
A silicone composition was obtained in the same manner as in Example 1, except that the components and contents of the silicone composition were as shown in Table 2.
[比較例３]
（プライマー層）
　プライマー組成物の成分及び含有量を表１に示したものとした以外は、比較例１と同様の操作をし、プライマー層を形成した。 [Comparative Example 3]
(primer layer)
A primer layer was formed in the same manner as in Comparative Example 1, except that the components and contents of the primer composition were as shown in Table 1.
（シリコーン層及び積層体）
　比較例１と同様の操作をし、シリコーン層及び積層体を形成した。 (Silicone layer and laminate)
The same operation as in Comparative Example 1 was performed to form a silicone layer and a laminate.
[比較例４]
（プライマー層）
　プライマー組成物の成分及び含有量を表１に示したものとした以外は、比較例１と同様の操作をし、プライマー層を形成した。 [Comparative Example 4]
(primer layer)
A primer layer was formed in the same manner as in Comparative Example 1, except that the components and contents of the primer composition were as shown in Table 1.
（シリコーン層及び積層体）
　比較例１と同様の操作をし、シリコーン層及び積層体を形成した。 (Silicone layer and laminate)
The same operation as in Comparative Example 1 was performed to form a silicone layer and a laminate.
＜膜厚＞
　上記で得られた積層体の膜厚は全て約３００μｍであった。 <Film thickness>
All of the laminates obtained above had a film thickness of about 300 μm.
＜ＳＰ値＞
　プライマー層のベースポリマーのＳＰ値（溶解度パラメータ）を、論文（R. F. Fedors: Polym. Eng. Sci., 14 〔2〕, 147-154 (1974)）に記載の凝集エネルギーＥおよびモル分子容Ｖを用いてＦｅｄｏｒｓ法から求めた。 <SP value>
The SP value (solubility parameter) of the base polymer of the primer layer is calculated from the cohesive energy E and molar molecular volume V described in the paper (R. F. Fedors: Polym. Eng. Sci., 14 [2], 147-154 (1974)). It was obtained from the Fedors method using
　具体的には、対象となる物質の分子全体の凝集エネルギー合計値ΣＥを、対象となる物質の分子全体のモル分子容合計値ΣＶで割って、平方根をとった値をＳＰ値とした。対象となる物質の分子全体の凝集エネルギー合計値ΣＥは、上記論文記載の各原子団の凝集エネルギーＥ（ｃａｌ／ｍｏｌ）をモル比で加重平均することによって求めることができる。また、対象となる物質の分子全体のモル分子容合計値ΣＶは、上記論文記載の各原子団のモル分子容Ｖ（ｃｍ３／ｍｏｌ）をモル比で加重平均することによって求めることができる。対象となる物質の各構成原子団のモル比率はフーリエ変換核磁気共鳴分光法分析を実施して、調べることができる。 Specifically, the SP value was obtained by dividing the total cohesive energy ΣE of the entire molecule of the target substance by the total molar molecular volume ΣV of the entire molecule of the target substance and taking the square root. The total cohesive energy ΣE of the entire molecule of the target substance can be obtained by taking the weighted average of the cohesive energies E (cal/mol) of the respective atomic groups described in the above paper by molar ratio. Further, the total molar molecular volume ΣV of the entire molecule of the target substance can be obtained by weighting the molar molecular volume V (cm 3 /mol) of each atomic group described in the above paper and averaging the molar ratio. The molar ratio of each constituent atomic group of the substance of interest can be determined by performing Fourier transform nuclear magnetic resonance spectroscopy analysis.
　ＳＰ値＝（分子全体の凝集エネルギーΣＥ／分子全体のモル分子容ΣＶ）１／２
　分子全体の凝集エネルギーΣＥ＝各構成原子団の凝集エネルギーＥをモル比で加重平均したもの
　分子全体のモル分子容ΣＶ＝各構成原子団のモル分子容Ｖをモル比で加重平均したもの SP value = (cohesion energy ΣE of whole molecule/molar molecular volume ΣV of whole molecule) 1/2
Cohesive energy ΣE of the whole molecule = Weighted average of cohesive energy E of each constituent atomic group by molar ratio Molar molecular volume of whole molecule ΣV = Weighted average of molar molecular volume V of each constituent atomic group by molar ratio
　なお、Ｆｅｄｏｒｓ法によるＳＰ値の計算例は以下のとおりである。 An example of calculating the SP value by the Fedors method is as follows.
［ポリエチレン（構成原子団はＣＨ２）］
構成原子団ＣＨ２の上記論文記載値は、凝集エネルギーＥ＝１１８０（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝１６．１（ｃｍ３／ｍｏｌ）
分子全体の凝集エネルギーΣＥ＝１１８０×１＝１１８０（ｃａｌ／ｍｏｌ）
分子全体のモル分子容ΣＶ＝１６．１×１＝１６．１（ｃｍ３／ｍｏｌ）
ＳＰ値＝（１１８０／１６．１）１／２＝８．５６（ｃａｌ／ｃｍ３）１／２ [Polyethylene (constituent atomic group is CH 2 )]
The values described in the above paper for the constituent atomic group CH 2 are cohesive energy E = 1180 (cal/mol), molar molecular volume V = 16.1 (cm 3 /mol).
Cohesive energy of the entire molecule ΣE = 1180 × 1 = 1180 (cal/mol)
Molecular volume of the whole molecule ΣV=16.1×1=16.1 (cm 3 /mol)
SP value=(1180/16.1) 1/2 =8.56 (cal/cm 3 ) 1/2
［ポリプロピレン（構成原子団はＣＨ２、ＣＨ、ＣＨ３）］
構成原子団ＣＨ２の上記論文記載値は、凝集エネルギーＥ＝１１８０（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝１６．１（ｃｍ３／ｍｏｌ）
構成原子団ＣＨの上記論文記載値は、凝集エネルギーＥ＝８２０（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝－１．０（ｃｍ３／ｍｏｌ）
構成原子団ＣＨ３の上記論文記載値は、凝集エネルギーＥ＝１１２５（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝３３．５（ｃｍ３／ｍｏｌ）
分子全体の凝集エネルギーΣＥ＝１１８０×（１／３）＋８２０×（１／３）＋１１２５×（１／３）＝１０４２（ｃａｌ／ｍｏｌ）
分子全体のモル分子容ΣＶ＝１６．１×（１／３）－１．０×（１／３）＋３３．５×（１／３）＝１６．２（ｃｍ３／ｍｏｌ）
ＳＰ値＝（１０４２／１６．２）１／２＝８．０２（ｃａｌ／ｃｍ３）１／２ [Polypropylene (Constituent atomic groups are CH 2 , CH, CH 3 )]
The values described in the above paper for the constituent atomic group CH 2 are cohesive energy E = 1180 (cal/mol), molar molecular volume V = 16.1 (cm 3 /mol).
The values described in the above paper for the constituent atomic group CH are cohesive energy E = 820 (cal/mol) and molar molecular volume V = -1.0 (cm 3 /mol).
The values described in the above paper for the constituent atomic group CH 3 are cohesive energy E = 1125 (cal/mol), molar molecular volume V = 33.5 (cm 3 /mol).
Cohesive energy of the whole molecule ΣE = 1180 x (1/3) + 820 x (1/3) + 1125 x (1/3) = 1042 (cal/mol)
Molecular volume of the whole molecule ΣV=16.1×(1/3)−1.0×(1/3)+33.5×(1/3)=16.2 (cm 3 /mol)
SP value = (1042/16.2) 1/2 = 8.02 (cal/cm 3 ) 1/2
［エチレンとプロピレンの比が１：１のエチレンプロピレンゴム（構成原子団はＣＨ２、ＣＨ、ＣＨ３）］
構成原子団ＣＨ２の上記論文記載値は、凝集エネルギーＥ＝１１８０（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝１６．１（ｃｍ３／ｍｏｌ）
構成原子団ＣＨの上記論文記載値は、凝集エネルギーＥ＝８２０（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝－１．０（ｃｍ３／ｍｏｌ）
構成原子団ＣＨ３の上記論文記載値は、凝集エネルギーＥ＝１１２５（ｃａｌ／ｍｏｌ）、モル分子容Ｖ＝３３．５（ｃｍ３／ｍｏｌ）
分子全体の凝集エネルギーΣＥ＝１１８０×（３／５）＋８２０×（１／５）＋１１２５×（１／５）＝１０９７（ｃａｌ／ｍｏｌ）
分子全体のモル分子容ΣＶ＝１６．１×（３／５）－１．０×（１／５）＋３３．５×（１／５）＝１６．２（ｃｍ３／ｍｏｌ）
ＳＰ値＝（１０４２／１６．２）１／２＝８．２３（ｃａｌ／ｃｍ３）１／２ [Ethylene-propylene rubber having a ratio of ethylene to propylene of 1:1 (constituent atomic groups are CH 2 , CH, CH 3 )]
The values described in the above paper for the constituent atomic group CH 2 are cohesive energy E = 1180 (cal/mol), molar molecular volume V = 16.1 (cm 3 /mol).
The values described in the above paper for the constituent atomic group CH are cohesive energy E = 820 (cal/mol) and molar molecular volume V = -1.0 (cm 3 /mol).
The values described in the above paper for the constituent atomic group CH 3 are cohesive energy E = 1125 (cal/mol), molar molecular volume V = 33.5 (cm 3 /mol).
Cohesive energy of the entire molecule ΣE = 1180 x (3/5) + 820 x (1/5) + 1125 x (1/5) = 1097 (cal/mol)
Molecular volume of the whole molecule ΣV=16.1×(3/5)−1.0×(1/5)+33.5×(1/5)=16.2 (cm 3 /mol)
SP value=(1042/16.2) 1/2 =8.23 (cal/cm 3 ) 1/2
＜評価＞
（温度応答ブリード）
　得られた積層体をペルチェ素子（株式会社ビップス社製、ＶＰＥ－３５）に乗せた。Ｎ２パージ（２Ｌ／ｍｉｎ）下で５℃から－１５℃まで１℃ずつ冷却していき（保持時間３分）、積層体表面からオイルがブリードしたものを〇（良好）、しなかったものを×（不良）とした。オイルのブリードは、マイクロスコープにて観察した。
　結果を表３に示す。 <Evaluation>
(Temperature responsive bleed)
The obtained laminate was placed on a Peltier element (VPE-35 manufactured by Bips Co., Ltd.). Cooled by 1°C from 5°C to -15°C under N2 purge ( 2 L/min) (retention time: 3 minutes). was set as x (defective). Oil bleeding was observed under a microscope.
Table 3 shows the results.
（密着性）
　密着（付着）性の評価は、ＪＩＳＫ－５６００－５－６（塗膜の機械的特性　付着性）を参考に実施した。
　具体的には、クロスカット試験カッターガイド（商品名「スーパーカッターガイド」、太佑機材株式会社製）、カッター、ポリイミド粘着テープ（ＮＯ．３６０ＵＬ、厚み０．０６ｍｍ×幅５０ｍｍ、日東電工株式会社製）を準備した。ポリイミド粘着テープにはシリコーン粘着剤が使用されており、シリコーン層と密着性が高いため選択した。 (Adhesion)
Adhesion (adhesion) property was evaluated with reference to JISK-5600-5-6 (mechanical properties of coating film adhesion property).
Specifically, a crosscut test cutter guide (trade name “Super Cutter Guide”, manufactured by Taiyu Kizai Co., Ltd.), a cutter, a polyimide adhesive tape (NO.360UL, thickness 0.06 mm × width 50 mm, manufactured by Nitto Denko Corporation) prepared. The polyimide adhesive tape uses a silicone adhesive and was selected because of its high adhesion to the silicone layer.
　得られた積層体をクロスカット試験カッターガイドを用いて、積層体のみに塗膜に対して垂直にカッターで４ｍｍ間隔で６本切込みを入れた。その後、方向を９０°変えて先ほどの切込みに直行するように６本切込みを入れた（計２５マス）。 Using a cross-cut test cutter guide, 6 cuts were made on the obtained laminate only with a cutter perpendicular to the coating film at intervals of 4 mm. After that, the direction was changed by 90° and 6 incisions were made so as to be perpendicular to the previous incisions (total of 25 squares).
　長さ約７５ｍｍにカットした透明付着テープを格子にカットした部分に張り付け、指でしっかりこすりつけ張り付けた。（格子の部分にかかった個所と最低２０ｍｍを超える長さで、指でテープを平らになるようにこすった）。テープが塗膜に正しく接触しているかテープを通してみられる塗膜の色で判断した。 A transparent adhesive tape cut to a length of about 75 mm was pasted on the part cut into the lattice, and then rubbed firmly with a finger to stick. (The tape was rubbed flat with a finger over the portion of the grid and a minimum length of 20 mm). Proper contact of the tape to the coating was judged by the color of the coating seen through the tape.
　テープを付着してから５分以内にテープを６０°に近い角度で端をつかみ０．５～１秒で確実に引き離した。密着性評価は、ＪＩＳ　Ｋ５６００－５－６に従い、０～５分類の６段階で評価を行い、０～１分類を〇（良好）、２～５分類を×（不良）とした。
　結果を表３に示す。 Within 5 minutes after the tape was applied, the tape was grasped by the edge at an angle close to 60° and pulled off securely in 0.5-1 second. Adhesion evaluation was performed according to JIS K5600-5-6, and evaluation was performed in six stages from 0 to 5, with 0 to 1 classified as ◯ (good) and 2 to 5 classified as × (poor).
Table 3 shows the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３の結果から、本発明の積層体は、プライマー層とシリコーン層の間の密着性に優れ、かつ優れた着氷及び／又は着雪防止機能を有することが分かった。 From the results in Table 3, it was found that the laminate of the present invention has excellent adhesion between the primer layer and the silicone layer, and has an excellent anti-icing and/or anti-snowing function.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０２１年３月２６日出願の日本特許出願（特願２０２１－０５３７９３）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2021-053793) filed on March 26, 2021, the content of which is incorporated herein by reference.
１　　積層体
１１　プライマー層
１２　シリコーン層
１３　基材 1 laminate 11 primer layer 12 silicone layer 13 base material

Claims (9)

  1. 　シリコーン層、及びプライマー層を有する積層体であって、
    　前記シリコーン層は、オイル成分、及び付加型シリコーン樹脂を含有し、
    　前記オイル成分は、温度が所定値以下に低下したとき前記シリコーン層から滲出することができ、
    　前記プライマー層は、前記付加型シリコーン樹脂と結合しているベースポリマーを含有する、積層体。     A laminate having a silicone layer and a primer layer,
    The silicone layer contains an oil component and an addition-type silicone resin,
    The oil component can exude from the silicone layer when the temperature drops below a predetermined value,
    The laminate, wherein the primer layer contains a base polymer bonded to the addition-type silicone resin.
  2. 　前記シリコーン層は、硬化触媒を含有する、請求項１に記載の積層体。 The laminate according to claim 1, wherein the silicone layer contains a curing catalyst.
  3. 　前記ベースポリマーは、ヒドロシリル基含有硬化剤由来の構造単位を介して前記付加型シリコーン樹脂と結合している、請求項１又は２に記載の積層体。 The laminate according to claim 1 or 2, wherein the base polymer is bonded to the addition-type silicone resin via a structural unit derived from a hydrosilyl group-containing curing agent.
  4. 　前記プライマー層を形成するプライマー組成物は、硬化触媒を含有する、請求項１～３のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the primer composition forming the primer layer contains a curing catalyst.
  5. 　前記プライマー層を形成するプライマー組成物は、ヒドロシリル基含有硬化剤を含有する、請求項１～４のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 4, wherein the primer composition forming the primer layer contains a hydrosilyl group-containing curing agent.
  6. 　前記ベースポリマーのＳＰ値は、７．５～１１．０（ｃａｌ／ｃｍ３）１／２である、請求項１～５のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 5, wherein the base polymer has an SP value of 7.5 to 11.0 (cal/cm 3 ) 1/2 .
  7. 　さらに基材を有する、請求項１～６のいずれか１項に記載の積層体。 The laminate according to any one of claims 1 to 6, further comprising a base material.
  8. 　ＳＰ値が７．５～１１．０（ｃａｌ／ｃｍ３）１／２であるベースポリマーを含有し、
    　ヒドロシリル基含有硬化剤及び硬化触媒からなる群から選択される少なくとも１種を含有する、プライマー組成物。     Containing a base polymer having an SP value of 7.5 to 11.0 (cal/cm 3 ) 1/2 ,
    A primer composition containing at least one selected from the group consisting of a hydrosilyl group-containing curing agent and a curing catalyst.
  9. 　ヒドロシリル基含有硬化剤と反応できる官能基を有する、請求項８に記載のプライマー組成物。 The primer composition according to claim 8, which has a functional group capable of reacting with a hydrosilyl group-containing curing agent.
PCT/JP2022/013131 2021-03-26 2022-03-22 Layered body and primer composition WO2022202807A1 (en)

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JPS5678960A (en) * 1979-12-03 1981-06-29 Toshiba Silicone Co Ltd Surface treatment of rubber
JPS60178046A (en) * 1984-02-24 1985-09-12 住友ベークライト株式会社 Composite molded shape of olefin group resin composition andsilicone rubber
JPS6116839A (en) * 1984-07-02 1986-01-24 Goyo Shiko Kk Manufacture of release paper
JPH05179159A (en) * 1991-06-13 1993-07-20 Dow Corning Corp Primer composition and method of top coating of silicone suprort
JPH05505845A (en) * 1990-03-27 1993-08-26 コートールズ　コーティングス　（ホールディングス）　リミティド coating composition
JPH0625615A (en) * 1992-04-07 1994-02-01 Shin Etsu Chem Co Ltd Primer composition
JPH09176520A (en) * 1995-12-21 1997-07-08 Nippon Zeon Co Ltd Primer composition and molded article having primer layer
JPH10214801A (en) * 1997-01-31 1998-08-11 Teijin Ltd Dicing tape
JP2000185369A (en) * 1998-12-21 2000-07-04 Mitsubishi Polyester Film Llc Silicone-coated film having anti-slip coating on its back surface and slip preventing method therefor
JP2001323210A (en) * 2000-03-08 2001-11-22 Kanegafuchi Chem Ind Co Ltd Primer composition and adhesion method
JP2002080783A (en) * 2000-09-11 2002-03-19 Kanegafuchi Chem Ind Co Ltd Primer composition and bonding method
JP2003084593A (en) * 2001-06-28 2003-03-19 Toho Kasei Kk Endless belt and manufacturing method therefor
JP2011524268A (en) * 2008-05-29 2011-09-01 ブルースター・シリコーンズ・フランス Articles that have antifouling properties and are used for underwater applications, especially marine applications
JP2012149240A (en) * 2010-12-31 2012-08-09 Dow Corning Toray Co Ltd Primer composition for silicone adhesive, laminate, and silicone adhesive tape
JP2015507667A (en) * 2011-12-22 2015-03-12 スリーエム イノベイティブ プロパティズ カンパニー Adhesive article including primer layer and method for producing the same
JP2018513881A (en) * 2015-03-05 2018-05-31 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition, use of the composition, and laminate made from the composition
JP2019511015A (en) * 2016-07-06 2019-04-18 エイチピー・インディゴ・ビー・ブイＨＰ Ｉｎｄｉｇｏ Ｂ．Ｖ． Release layer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5678960A (en) * 1979-12-03 1981-06-29 Toshiba Silicone Co Ltd Surface treatment of rubber
JPS60178046A (en) * 1984-02-24 1985-09-12 住友ベークライト株式会社 Composite molded shape of olefin group resin composition andsilicone rubber
JPS6116839A (en) * 1984-07-02 1986-01-24 Goyo Shiko Kk Manufacture of release paper
JPH05505845A (en) * 1990-03-27 1993-08-26 コートールズ　コーティングス　（ホールディングス）　リミティド coating composition
JPH05179159A (en) * 1991-06-13 1993-07-20 Dow Corning Corp Primer composition and method of top coating of silicone suprort
JPH0625615A (en) * 1992-04-07 1994-02-01 Shin Etsu Chem Co Ltd Primer composition
JPH09176520A (en) * 1995-12-21 1997-07-08 Nippon Zeon Co Ltd Primer composition and molded article having primer layer
JPH10214801A (en) * 1997-01-31 1998-08-11 Teijin Ltd Dicing tape
JP2000185369A (en) * 1998-12-21 2000-07-04 Mitsubishi Polyester Film Llc Silicone-coated film having anti-slip coating on its back surface and slip preventing method therefor
JP2001323210A (en) * 2000-03-08 2001-11-22 Kanegafuchi Chem Ind Co Ltd Primer composition and adhesion method
JP2002080783A (en) * 2000-09-11 2002-03-19 Kanegafuchi Chem Ind Co Ltd Primer composition and bonding method
JP2003084593A (en) * 2001-06-28 2003-03-19 Toho Kasei Kk Endless belt and manufacturing method therefor
JP2011524268A (en) * 2008-05-29 2011-09-01 ブルースター・シリコーンズ・フランス Articles that have antifouling properties and are used for underwater applications, especially marine applications
JP2012149240A (en) * 2010-12-31 2012-08-09 Dow Corning Toray Co Ltd Primer composition for silicone adhesive, laminate, and silicone adhesive tape
JP2015507667A (en) * 2011-12-22 2015-03-12 スリーエム イノベイティブ プロパティズ カンパニー Adhesive article including primer layer and method for producing the same
JP2018513881A (en) * 2015-03-05 2018-05-31 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition, use of the composition, and laminate made from the composition
JP2019511015A (en) * 2016-07-06 2019-04-18 エイチピー・インディゴ・ビー・ブイＨＰ Ｉｎｄｉｇｏ Ｂ．Ｖ． Release layer

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