JP3021746B2 - Fluorine-containing block copolymer containing unsaturated group, method for producing the same, and active energy ray-curable material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing block copolymer having an unsaturated group which is sensitive to active energy rays such as ultraviolet rays and electron beams, a method for producing the same, and a method for producing active energy rays. In addition, the present invention relates to an active energy ray curing material that exhibits the function of fluorine.

[0002]

2. Description of the Related Art The present inventors have previously proposed that a fluorine-containing block copolymer is useful as a surface modifier for a polymer material. For example, in Japanese Patent Application Laid-Open No. 60-22410, when a fluorine-containing block copolymer is added to a polymer material, the fluorine-containing block copolymer is oriented on the surface, and the material surface has excellent water repellency having a perfluoroalkyl group. It shows that excellent properties such as oil repellency and antifouling property can be imparted, and that the modifying effect has excellent durability. It is also known to be useful as an antiblocking agent (JP-A-2-4877) and as a moisture-proofing agent (JP-A-2-4877).
No. 4812).

[0003] In addition to thermoplastic resins and thermosetting resins, active energy ray-curable resins are often required to be imparted with properties such as water repellency, oil repellency, anti-blocking properties and moisture resistance. For example, UV-curable inks used for printing plastic bottles and the like are required to have water resistance, and solder resist materials and the like are required to have moisture-proof properties. The present inventors have proposed that a fluorine-containing block copolymer is useful as a modifier for such a material (Japanese Patent Application Laid-Open No. 2-4812).

[0004] There have been numerous proposals for materials having sensitivity to active energy rays.
There has also been proposed an active energy ray-sensitive type fluorine-containing block copolymer intended to be used as a resist material or a coating material. For example, JP-A-58-215411 proposes that a fluorine-containing sensitive material can be obtained by a radical copolymerization reaction between a monomer having photodimerization reactivity in a side chain and a fluorine-containing monomer. ing.

[0005] Japanese Patent Application Laid-Open Nos.
In JP-A-301268, a polymer which can be cured with an active energy ray is obtained by a reaction between a fluorine-containing polymer obtained by copolymerization of a hydroxyl group-containing vinyl ether and a fluoroolefin, and a compound having an isocyanate group and an unsaturated group. It is disclosed that. Further, Japanese Unexamined Patent Publication
In JP-A-2-190264, a coating composition containing a polymer obtained by a reaction between three components of a fluorine-containing block copolymer having an OH group, an isocyanate compound, and a compound having an OH group and an unsaturated group is disclosed. Is disclosed.

[0006]

As described above, it is possible to modify the surface of an active energy ray-curable resin with a fluorine-containing block copolymer having excellent surface orientation. In this case, the good continuity of the modifying effect is achieved by the entanglement effect of the polymer of the fluorine-free polymer portion, which is one polymer chain of the fluorinated block copolymer, and the resin to be modified. However, if both can be covalently bonded, the durability is further improved.

When the fluorinated block copolymer is used alone as a coating material, the fluorinated polymer portion is oriented at a high density on the air side surface, and the fluorine-free polymer portion is high on the substrate side. Since the film is oriented to the density, a function derived from the fluoropolymer portion can be imparted to the film surface while maintaining good adhesion. If the sensitivity to active energy rays can be further developed while taking advantage of this property, application as various resist materials having a fluorine function can be expected.

Japanese Patent Application Laid-Open No. 62-190264 has already proposed a fluorine-containing block copolymer containing an unsaturated group. However, in this proposal, since a method of introducing an unsaturated group by a reaction using an isocyanate compound is employed, there is a problem that gelation easily occurs during the reaction. For the fluorine-containing block copolymer and the unsaturated group-containing compound, the gelation tends to be suppressed by using a large amount of the isocyanate compound, but when synthesized using such a large amount of the isocyanate compound, the fluorine-containing There is a problem that the molecular weight increases as the amount of the block copolymer increases and the ratio of the fluoropolymer portion decreases, so that the surface performance tends to decrease.

In the case of utilizing for a specific application as in this proposal, even if the function of the fluorinated block copolymer is exhibited, it is necessary to use a surface-modifying agent widely for use as a surface modifier of an active energy ray-curable resin. There was a problem in terms of activity, and further improvement was desired. In addition, when the polymer obtained by this method is used for a resist material or the like, the surface orientation of the fluoropolymer portion tends to be low, and the active energy ray non-irradiated portion also has a net objective of increasing the molecular weight. Therefore, there is a problem that developability is not always good for various developers.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has as its object to miscibility with other resins, water / oil repellency of a surface, adhesion to a substrate, and sensitivity to an active energy ray. An object of the present invention is to provide a fluorine-containing block copolymer having an unsaturated group having a property and a method for producing the same. Another object of the present invention is to provide a material for curing an active energy ray, which is made of the fluorine-containing block copolymer, is sensitive to an active energy ray, and has excellent curability.

[0011]

In order to achieve the above object, according to a first aspect of the present invention, there is provided a polymer portion derived from the above formula (1).
And a structural unit (B) consisting of a polymer portion derived from Chemical formula 11 and a polymer portion having Chemical formula 35 or Chemical formula 47 as a unit, and the structural unit (A) / The ratio of the structural unit (B) is 80/2 by weight.
0 to 10/90, the viscosity of a solution adjusted to 30% by weight by dissolving or dispersing in a non-fluorinated organic solvent which is a good solvent for the structural unit (B) is 0.05 to 7 poise at 25 ° C. The gist is a fluorine-containing block copolymer containing an unsaturated group.

According to a second aspect of the present invention, in the first aspect, the structural unit (A) is at least 40% by weight of the polymer portion derived from the chemical formula (1) and the polymer portion 60 derived from the chemical formula (11). The gist of the present invention is a fluorine-containing block copolymer containing an unsaturated group consisting of not more than% by weight. In the third invention, a structural unit (A) derived from the chemical formula _{1 and a} structural unit (B ₁ ) composed of a polymer portion derived from the chemical formula 11 and a polymer portion derived from the following chemical formula 53 A fluorine-containing block copolymer or a structural unit (A) comprising at least 40% by weight of a polymer portion derived from Chemical Formula 1 and at most 60% by weight of a polymer portion derived from Chemical Formula 11; By reacting a fluorine-containing block copolymer consisting of a structural unit (B ₁ ) consisting of a polymer part derived from The gist is a method for producing a fluorine-containing block copolymer containing an unsaturated group according to the first or second invention for producing a fluorine-containing block copolymer containing an unsaturated group based on a hydrochloric acid reaction. .

Further, in the fourth invention, a structural unit (A) comprising a polymer portion derived from the above-mentioned chemical formula 1, a polymer portion derived from the above-mentioned chemical formula 11, and a polymer derived from the above-mentioned chemical formula 55 Or a fluorine-containing block copolymer comprising a structural unit (B ₂ ) comprising at least 40% by weight of a polymer portion derived from the above formula 1 and 60% by weight or less of a polymer portion derived from the above formula 11. Structural unit (A)
And a polymer moiety derived from Chemical Formula 11 and Chemical Formula 5
By reacting a fluorine-containing block copolymer comprising a structural unit (B ₂ ) derived from Formula 5 with a compound represented by the above formula, a fluorine-containing block copolymer containing an unsaturated group based on a dehydrochlorination reaction. First invention or second invention for producing polymer
The gist of the invention is a method for producing a fluorine-containing block copolymer containing an unsaturated group.

In a fifth aspect, the gist of the present invention is an active energy ray-curable material comprising the block copolymer of the first aspect or the second aspect and curable by an active energy ray. Next, the present invention will be described in detail. First, the structural unit (A) in the block copolymer of the present invention will be described. In order for the block copolymer to be sufficiently surface-active and exhibit its function as a fluorinated polymer, this structural unit is a polymer derived from Chemical Formula 1 or derived from Chemical Formula 1. It is essential that the polymer portion comprises at least 40% by weight and the polymer portion derived from the above formula 11 at most 60% by weight.
A polymer moiety 4 in which the structural unit (A) is derived from the chemical formula 1
When the content is less than 0% by weight, the surface activity is reduced and the function as a surface modifier is insufficient. Further, even when a film is formed from the block copolymer of the present invention solely for use as a resist material, the function of fluorine on the surface is reduced.

In the above formula (1), if p and m are more than 10, the properties derived from the perfluoroalkyl group are undesirably reduced. Further, the monomer in which n and i exceed 16 is
The synthesis is not easy, and the properties derived from the perfluoroalkyl group are not always good, which is not preferable. p
Is 1-4, m is 0-4, n and i are 1-10,
Moreover terminal perfluoroalkyl group is more preferable that a -CF _3.

The following compounds can be used as the monomer represented by the above formula (1).

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In addition to the above monomers, the following monomers can also be used.

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[0047]

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One or more of these monomers are appropriately selected and used. Next, the monomer represented by Chemical Formula 11 is used to constitute the structural unit (A) in the second, third, fourth, and fifth inventions, and is used in the first to fifth inventions. It is indispensable to constitute the unit (B). Chemical formula 11
Specific examples of the monomer represented by are methyl acrylate and / or methyl methacrylate [hereinafter collectively referred to as methyl (meth) acrylate]. The same applies hereinafter), ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth)
Isopropyl acrylate, glycidyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Octyl acid, lauryl (meth) acrylate, (meth)
(Meth) acrylates such as stearyl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, -N, N-dimethylaminoethyl (meth) acrylate, hydroxylethyl (meth) acrylate, (meth) ) Hydroxypropyl acrylate, (meth)
Hydroxyesters of (meth) acrylic acid such as 3-chloro-2-hydroxypropyl acrylate, triethylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate Esters of polyethylene glycol and polypropylene glycol, aromatic vinyl-type monomers such as styrene, vinyltoluene and α-methylstyrene; carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate and vinyl stearate; (meth) acrylamide; N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N
-(Meth) acryloylmorpholine, vinyl monomers containing an amide group such as 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid, and itaconic acid. One or more of these monomers are appropriately selected and used.

Next, the structural unit (B) in the block copolymer of the present invention will be described. The structural unit (B) is
In order to exhibit sensitivity to active energy rays, it is indispensable to use Chemical Formula 35 or Chemical Formula 47 as a constituent. The proportion in the structural unit (B) is preferably 1 to 9
Within the range of 8% by weight, it is appropriately determined according to the purpose of use of the block copolymer of the present invention and the type of unsaturated group. In any of the unsaturated groups, the proportion occupied by Chemical Formula 35 is 1
If the weight% is not reached, the sensitivity tends to be insufficient.

In the case where Chemical Formula 38 or Chemical Formula 39 is selected as an unsaturated group, an appropriate sensitivity may be expressed in a region where the chemical compound 35 is present in a high proportion.
If it exceeds 8% by weight, the adhesion to the substrate, the developability and the like tend to decrease. In addition, it is more appropriate for the unsaturated group to be present in an amount of 20% by weight or more in order to express sufficient sensitivity.

When the unsaturated group is Chemical formula 40, Chemical formula 41, Chemical formula 42 or Chemical formula 43, the ratio occupied by Chemical formula 35 or Chemical formula 47 is 3-7.
A range of 0% by weight is more appropriate. When t in Chemical Formula 35 exceeds 20, the properties of the fluorinated group such as water and oil repellency of the fluorinated block copolymer are impaired, and the adhesion to a substrate or the like is also reduced. In the case where the unsaturated group is chemical formula (48), chemical formula (49) or chemical formula (50), the ratio of chemical formula (47) is more preferably in the range of 3 to 70% by weight.

Further, the structural unit (B) is provided with good adhesion to a substrate, film formability, and developability by constituting the structural unit (B) as an essential component. Also,
When used as a surface modifier for an active energy ray-curable resin, it contributes to exhibiting good miscibility with the resin. Next, the weight ratio of the structural unit (A) to the structural unit (B) in the block copolymer of the present invention is 80 / 20-1.
0/90. If the ratio of the structural unit (A) exceeds 80% by weight, the sensitivity to active energy rays decreases and the adhesion to a substrate decreases, which is not preferable. Further, when used as a surface modifier for an active energy ray-curable resin, a problem may occur in the miscibility with the resin. On the other hand, when the ratio of the structural unit (A) is less than 10% by weight, the function of fluorine derived from the structural unit (A) cannot be sufficiently exhibited. In particular, when used as a surface modifier for an active energy ray-curable resin, the surface orientation is insufficient.

As for the molecular weight of the fluorine-containing block copolymer of the present invention, it is difficult to select a common good solvent for the structural unit (A) and the structural unit (B), and it is difficult to measure a true value. The range can be set by the polymer solution viscosity.
That is, dimethylformamide (hereinafter referred to as DMF)
Alternatively, the viscosity of a solution adjusted to 30% by weight by dissolving or dispersing in methyl ethyl ketone (hereinafter referred to as MEK) is 25 ° C.
Must be 0.05 to 7 poise.
When it is less than 0.05 poise, film formability and developability are reduced when the block copolymer of the present invention is used for a resist material or the like. If it exceeds 7 poise, the surface orientation becomes insufficient, particularly when used as a surface modifier for active energy ray-curable resins.

Next, the method for producing the fluoropolymer portion having an unsaturated group of the present invention will be described. First, the structural unit (B ₁ ) or (B
₂ ) A fluorine-containing block copolymer having the structural unit (A) is synthesized. As this method, in particular, from the viewpoints of industrial productivity and ambiguity in terms of performance, polymeric peroxide having two or more peroxy bonds in one molecule and two or more azo bonds in one molecule. It is preferably produced by radical polymerization using a polyazo compound as a polymerization initiator. As the polymerization method, the structural unit is represented by (B ₁ )
In such a case, a usual bulk polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method or the like is employed. In addition, the structural unit is (B
_In the case of ₂ ), a bulk polymerization method, a solution polymerization method, or the like is adopted.

Polymeric peroxide is used as a polymerization initiator.
The manufacturing method in the case of
You. First, using polymeric peroxide, the structural unit
(B ₁) Or (B_Two) To form
Of the monomer and the monomer represented by the above formula 53 or 55
By performing the polymerization reaction, a peroxy bond is formed in the chain.
The introduced peroxy bond-containing vinyl polymer is obtained. This
In addition, a unit represented by the above formula 1 for forming the structural unit (A)
And a mixture of the monomer and
When the combination is performed, the peroxy bond contains
Cleavage at the bond yields an efficient block copolymer
It is.

Next, the block copolymer having the structural unit (B ₁ ) or (B ₂ ) and the structural unit (A) and the compound represented by the above formula (54) or (60) are dehydrochlorinated to obtain an unsaturated compound. A fluorinated block copolymer into which a group has been introduced is obtained. The reaction conditions are such that the ratio of the amount of the OH group contained in the structural unit (B ₁ ) in the block copolymer to the chemical formula is 1 / 0.3 to 1 / 1.3 in terms of mol. Is appropriate.

Further, the compound represented by the formula (B ₂ )
The ratio of the amount of 7 groups to the compound of formula 60 is 1/1 to 1/1.
3 is appropriate. In the case of the structural unit (B ₁ ), if the ratio of Chemical formula 54 is less than 0.3, an unnecessary OH group is contained in the fluorinated block copolymer, and is expressed in the structural unit (A). In some cases, such properties as water and oil repellency may be impaired.

The higher the abundance ratio of the chemical compound 54 is, the more excellent the reactivity can be expressed. However, the step of removing the excessive charge amount after the completion of the reaction becomes complicated. For this reason, 1.3
It is appropriate not to exceed. In the case of the structural unit (B ₂ ), when the ratio of Chemical Formula 60 is less than 1,

[0079]

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It is not preferable because the group remains. If it is less than 0.3, an unnecessary OH group will be contained in the fluorine-containing block copolymer, which may impair properties such as water and oil repellency exhibited by the structural unit (A). Not preferred. The above Chemical Formula 60 can exhibit better reactivity as its abundance ratio is higher, however, it is not preferable because water and oil repellency and the like may be impaired by excessive Chemical Charge 60 after completion of the reaction.

The reaction temperature is suitably from 10 to 60 ° C. in order to achieve sufficient reactivity and to prevent the block copolymer from becoming high in molecular weight by the thermal polymerization of unsaturated groups. As a method of dehydrochlorination, a known method such as the presence of pyridine or the like in the reaction system and precipitation as a hydrochloride, or bubbling with nitrogen gas or the like, and discharging the generated hydrochloric acid gas can be employed. . Because this reaction is very fast and exothermic, care must be taken in controlling the reaction.

Incidentally, Chemical Formulas 54 and 55 can be obtained and used as commercial products, or can be synthesized and used according to a known method. The composition analysis of the fluorine-containing block copolymer containing an unsaturated group of the present invention was carried out by NM
It can be performed by known means such as R, IR and elemental analysis. Next, the active energy ray curing material refers to a material which has sensitivity to active energy rays and is cured by the active energy rays. Specifically, a surface modifier which improves the surface properties of the active energy ray-curable resin by adding the block copolymer of the present invention to a resist material or an active energy ray-curable resin, which is a main component, and the like can be given. .

[0083]

EXAMPLES Examples embodying the present invention will be described below in comparison with comparative examples. In the examples and comparative examples, “parts” indicates “parts by weight” and “%” indicates “% by weight”. Example 1 (1) Synthesis of Peroxy Bond-Containing Polymer ME was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser.
Charge 75 parts of KMF and 75 parts of DMF and heat to 70 ° C. while blowing in nitrogen gas.
Parts, methyl methacrylate (hereinafter referred to as MMA) 120
Parts, hydroxyethyl methacrylate (hereinafter, referred to as HEMA) 80 parts,

[0084]

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A mixed solution consisting of 15 parts was charged over 2 hours, and a polymerization reaction was further performed for 4 hours to obtain a solution of a peroxy bond-containing polymer. The polymerization conversion of MMA and HEMA is
As a result of measuring the amount of residual monomers by gas chromatography (hereinafter referred to as GC), all were 97% or more.
This polymer solution was diluted 4 times with DMF and then poured into a large excess of hexane with stirring to reprecipitate the polymer. The precipitated polymer was sufficiently dried to obtain a powdery polymer. As a result of GC analysis, it was confirmed that no monomer remained. The active oxygen content of this powdery polymer was 0.13%, and the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC) was 15,000. (2) Synthesis of block copolymer Powdery acrylic polymer 28 obtained in (1) above
A mixed solution of 12 parts by mass, 61 parts by mass and 60 parts of DMF was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and a polymerization reaction was carried out at 70 ° C. for 10 hours while blowing nitrogen gas. The polymerization conversion of the fluorine monomer was 98%.

The obtained polymer solution was diluted with DMF to a 4-fold volume and poured into a large excess of water with stirring to reprecipitate the polymer. The precipitated polymer was sufficiently dried to obtain a powdery polymer. 30 parts of this fine powder is mixed with 450 parts of methanol.
Parts and a mixed solvent consisting of 150 parts of butyl acetate.
The mixture was stirred at 0 ° C. for 8 hours to extract a fluorine-free acrylic polymer which was one of the by-product components. Then, the remaining polymer was washed with trichlorotrifluoroethane 60.
0 parts and stirred at 40 ° C. for 48 hours to extract a fluoropolymer.

As a result, the above-mentioned powder was converted to a block copolymer /
It was found that the composition ratio of the acrylic polymer containing no fluorine / fluorine-containing polymer was 7.0 / 2.4 / 0.6. Therefore, the weight ratio of the fluorine-containing polymer portion [structural unit (A)] to the fluorine-free polymer portion [structural unit (B ₁ )] in the block copolymer is as follows:
It is determined as follows.

That is, the block copolymer was 28 parts (28 parts of the acrylic polymer and the fluorine monomer
70% of the total amount of 12 parts of 1), and the homopolymer is 12 parts. Of these, 2.4 parts of fluoropolymer (12 parts)
Of the acrylic polymer is 9.6 parts (80% of 12 parts). Therefore, in the block copolymer, the fluorinated segment is 9.6 parts (12 parts minus 2.4 parts), and the acrylic segment is 18.2 parts.
4 parts (28 parts minus 9.6 parts). Therefore, the weight ratio of the fluorine-containing polymer portion [structural unit (A)] and the fluorine-free polymer portion [structural unit (B ₁ )] in the block copolymer is 34/66 (9.6 / 1).
8.4).

Further, the block copolymer was replaced with deuterium-substituted DM.
As a result of NMR analysis using F, the constituent components of the polymer portion containing no fluorine were MMA / HEM as charged.
A was found to be 60/40. (3) Introduction reaction of unsaturated group into block copolymer In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 5 parts of the block copolymer obtained in the above (2), 15 parts of MEK,
1.58 parts of pyridine (O contained in the block copolymer)
(2 times the molar amount of the H group) to prepare a polymer solution. Then, while blowing nitrogen gas, at 50 ° C., 0.455 parts of acrylic acid chloride (0.5 times the molar amount of OH groups contained in the block copolymer) and MEK1.5
45 parts of the mixed solution was added dropwise over 30 minutes.
For 2 hours.

After the reaction, the pyridine hydrochloride was removed by filtration, and the polymer solution was diluted to 3 times with MEK and poured into a large excess of water / methanol (1/1 mixed solution) with stirring.
The polymer was reprecipitated and purified. After sufficiently drying the polymer powder, GPC analysis using DMF as an eluent showed that low-molecular compounds such as pyridine and acrylic acid chloride were almost completely removed.

[0091] polymers prepared were added 20% solution of DMF, result of IR measurement was deposited after sufficiently dried on a transparent plate of KBr, from 40 groups of around 1640 cm ^-1 Characteristic absorption was observed, and it was confirmed that unsaturated groups were introduced. In addition, as a result of NMR analysis using deuterium-substituted DMF, a proton peak derived from the chemical group 40 was newly generated around 6.4 ppm, and the HEMA component

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It was found that the proton peak (3.8 and 4.2 ppm) derived from the group was reduced. From the peak area ratio in consideration of the methyl ester proton peak (3.6 ppm) of the MMA component, the HEMA component before the reaction was converted.
It became clear that 50% of the 9 groups were replaced by the 52 groups. As a result, in the polymer obtained by this reaction, the ratio of the polymer portion having the formula 35 as the unit in the structural unit (B) was 26%, and the structural unit (A) / the structural unit (B)
Was 32/68 by weight.

A 30% solution prepared by adding DMF to the polymer powder had the appearance of a bluish white dispersion, and had a viscosity of 0.8 poise at 25 ° C. Example 2 (1) Synthesis of Peroxy Bond-Containing Polymer ME was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser.
K150 parts, 70 ° C while blowing nitrogen gas
And 135 parts of MEK, 120 parts of MMA,

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80 parts (hereinafter referred to as HEMA-CF),
A mixed solution consisting of 150 parts of the above Chemical Formula 88 was charged over 2 hours, and a polymerization reaction was further performed for 4 hours to obtain a solution of a peroxy bond-containing polymer. The polymerization conversion of MMA and HEMA-CF was 97% or more as a result of measuring the amount of residual monomer by GC. This polymer solution was diluted 4 times with MEK and then poured into a large excess of hexane with stirring to reprecipitate the polymer. The precipitated polymer was sufficiently dried to obtain a powdery polymer. GC
As a result of the analysis, it was confirmed that no monomer remained. The active oxygen content of this powdery polymer was 0.13%,
The number average molecular weight in terms of polystyrene measured by PC is 15
000. (2) Synthesis of Block Copolymer A mixed solution of 28 parts of the powdery polymer obtained in (1), 12 parts of Chemical Formula 61 and 60 parts of MEK was reacted with a thermometer, a stirrer, and a reflux condenser. The polymerization reaction was carried out at 70 ° C. for 10 hours while introducing nitrogen gas into the vessel. The polymerization conversion of the fluorine monomer was 98%.

The obtained polymer solution was diluted to 4 times with MEK and poured into a large excess of hexane with stirring to reprecipitate the polymer. The precipitated polymer was sufficiently dried to obtain a powdery polymer. 30 parts of this fine powder is butyl acetate 60
The mixture was poured into a mixed solvent of 0 parts and stirred at 50 ° C. for 8 hours to extract a fluorine-free acrylic polymer which is one of the by-product components. Next, the remaining polymer was charged into 600 parts of trichloroethane trifluoroethane,
The mixture was stirred at 40 ° C. for 48 hours to extract the fluorinated block copolymer.

As a result, it was found that the powder had a block copolymer / acrylic polymer not containing fluorine / fluorine-containing polymer composition ratio of 7.0 / 2.4 / 0.6. all right. Therefore, calculation was performed in the same manner as in Example 1, and the weight ratio of the fluorine-containing polymer portion [structural unit (A)] to the polymer portion not containing fluorine [structural unit (B ₁ )] in the block copolymer was 34. / 66.

Further, the block copolymer was replaced with deuterium-substituted DM.
As a result of NMR analysis using F, the constituent components of the polymer portion containing no fluorine were charged to MMA / KEM
A-CF was found to be 60/40. Then N /
0.06 g of the block copolymer fine powder was weighed and dispersed in 99% ethyl alcohol neutralized with a 10% sodium hydroxide solution, and neutralized and titrated with an N / 10 sodium hydroxide solution. As a result, the chlorine content of the block copolymer was found to be about 4.8%, and it was found that chlorides were introduced at the theoretical value.

(3) Introduction reaction of unsaturated group into block copolymer In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 5 parts of the block copolymer obtained in the above (2), 15 parts of MEK Was added to prepare a polymer solution. Then, while blowing nitrogen gas at 50 ° C., 1.16 parts of HEMA (1.3 times the amount of chloride contained in the block copolymer) and 1.1 parts of pyridine (of the amount of chloride contained in the block copolymer) A mixed solution of 2.times.) And 4.64 parts of MEK was added dropwise over 30 minutes, and the mixture was further reacted at 50 ° C. for 2 hours.

After the reaction, the pyridine hydrochloride was removed by filtration, and the polymer solution was diluted with DMF to a three-fold amount and poured into a large excess of water / methanol (1/1 mixed solution) with stirring to recycle the polymer. Precipitation and purification were performed. After sufficiently drying the polymer powder, GPC analysis using DMF as an eluent revealed that low-molecular compounds such as pyridine and HEMA were almost completely removed.

MEK was added to the polymer to prepare a 20% solution. The film was formed on a KBr transparent plate, dried sufficiently, and subjected to IR measurement. As a result, it was found that the compound was derived from the compound 41 at around 1640 cm ^-1. Characteristic absorption was observed, and it was confirmed that the unsaturated group was introduced. NMR analysis using deuterium-substituted DMF showed that 100% of the above-mentioned compound was introduced.

As a result, in the polymer obtained by this reaction, the ratio of the polymer portion having the formula 35 to the structural unit (B) was 50% by weight, and the ratio of the structural unit (A) / the structural unit ( The proportion of B) was shown to be 30/70 by weight. The solution prepared by adding MEK to this polymer powder and adjusted to 30% by weight had the appearance of a bluish white dispersion, and had a viscosity of 0.8 poise at 25 ° C. (Examples 3 to 6) Reaction of the block copolymer obtained in (2) of Example 1 with a chlorine compound shown in Table 1 using the same reactor as in (3) of Example 1. Thus, an unsaturated group introduction reaction of the block copolymer was performed.

The reaction was carried out according to (3) of Example 1, by dropping the dropping solution shown in Table 1 into the polymer solution shown in Table 1 under the same conditions as in Example 1, and continuing the reaction. went. The method of analyzing the polymer after the reaction is as described in (3) of Example 1.
Is the same as Tables 1 and 2 show the purification conditions, the analysis results of the polymer, and the DMF solution viscosity of the polymer.

[0105]

[Table 1]

The chlorine compounds in Table 1 represent the following. (1)

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(2) Chemical formula 90, (3)

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[0110]

[Table 2]

The mixed solvent in Table 2 was methanol / water = 1.
/ 1 represents a mixed solvent. (Examples 7 to 10) Using the same reactor as in Example 2 (3), the block copolymer obtained in Example 2 (2) and the OH group-containing compound shown in Table 3 were used. The reaction of introducing an unsaturated group into the block copolymer was carried out.

The reaction was carried out according to (3) of Example 2 by dropping the dropping solution shown in Table 3 into the polymer container shown in Table 3 under the same conditions as in Example 2, and further continuing the reaction. went. The method for analyzing the polymer after the reaction is described in Example 2, (3).
Is the same as The purification conditions, the analysis results of the polymer, and the DMF solution viscosity of the polymer are shown in Tables 3 and 4.

[0113]

[Table 3]

The OH group-containing compounds in Table 3 represent the following. (1)

[0115]

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(2)

[0117]

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(3)

[0119]

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[0120]

[Table 4]

(Examples 11 to 15) (1) Synthesis of Peroxy Bond-Containing Polymer Using the same reactor as used in Example 1, 300 parts of DMF was charged into the reactor, and nitrogen was blown into the reactor.
Heat to 0 ° C, 280 parts of MEK, ethylene glycol methacrylate monoester (Blenmer PE manufactured by NOF Corporation)
A mixed solution consisting of 200 parts of 200, EO repeating unit n = 4.5), 200 parts of n-butyl methacrylate, and 40 parts of n-butyl methacrylate was charged over 2 hours, and further subjected to a polymerization reaction for 3 hours to obtain a peroxy bond-containing polymer. A coalescence was obtained. As a result of measuring the amount of residual monomer by GC, the polymerization conversion was 98% or more. (2) Synthesis of Block Copolymer Composition A predetermined amount of the peroxy bond-containing polymer solution synthesized in (1) shown in Table 5 was charged into the same reactor as above. Then, a mixed solution of the monomer and DMF shown in Table 5 was dropped at 70 ° C. over 30 minutes while blowing nitrogen gas.
Further, a polymerization reaction was performed at 70 ° C. for 10 hours. As a result of GC analysis, the polymerization conversion of the monomer was 98%. (3) Introduction reaction of unsaturated group The polymer solution synthesized in the above (2) was diluted with MEK,
It was adjusted so that the active ingredient concentration became 20%. Then
In the same manner as in Example 2, pyridine was further added to 120 parts of the 20% solution to prepare a polymer solution. And Table 6
Was added dropwise at 50 ° C. over 30 minutes, and the mixture was further reacted at the same temperature for 3 hours to perform an unsaturated group introduction reaction. After the reaction, pyridine hydrochloride was removed by filtration, and the polymer solution was diluted with DMF to three-fold volume and poured into a large excess of methanol with stirring to reprecipitate and purify the polymer.

GPC analysis of the sufficiently dried polymer powder in the same manner as in Example 1 showed that none of the polymers contained a low molecular weight compound. In addition, IR analysis showed that an unsaturated group had been introduced, and NMR analysis showed that all of the OH groups in the polymer had disappeared and that an unsaturated group had been newly introduced. 10 parts of each polymer powder was added to a mixed solvent consisting of 100 parts of methanol and 200 parts of toluene.
After stirring for an hour, an acrylic polymer (containing unsaturated groups) containing no fluorine, which is one of the by-product components, was extracted. Next, the remaining polymer was added to 600 parts of trichloroethane trifluoroethane, and stirred at 40 ° C. for 48 hours to extract a fluoropolymer. The weight of the extract was measured to determine the constituent ratio of block copolymer / fluorine-free acrylic polymer / fluorine-containing block copolymer in the powder.

In addition, the fluoropolymer portion [Structural unit (A)] and the fluorine-free polymer portion [Structural unit (B)] of the block copolymer were compared with the unsaturation introduction ratio by NMR analysis. The weight ratio was calculated. further,
The block copolymer after the by-product extraction was dissolved and dispersed in deuterium-substituted acetone, and subjected to NMR analysis. According to the same method as in Example 1, the polymer portion having the chemical formula 35 as a unit in the structural unit (B) was used. The ratio was determined. Also, 25% of a 30% by weight solution prepared by adding DMF to the block copolymer powder was used.
The viscosity at ° C was measured.

Tables 5 and 6 show the results.

[0125]

[Table 5]

The fluorine-containing monomers in Table 5 represent the following. (1)

[0127]

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(2)

[0129]

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[0130]

[Table 6]

The chlorine compounds in Table 6 represent the following. (1)

[0132]

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(2)

[0134]

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Note (1) indicates the ratio of block copolymer / fluorine-free polymer / fluorine-containing polymer. (Examples 16 and 17) (1) Synthesis of block copolymer Using the same reactor as used in Example 1, 150 parts of MEK was charged into the reactor, and 7 parts were blown while blowing nitrogen gas.
Heated to 0 ° C., 204 parts of MEK, 100 parts of MMA, 90 parts of n-butyl methacrylate (n-BMA), HEMA1
A mixed solution consisting of 0 parts and 17 parts of the above-mentioned Chemical Formula 88 was charged over 2 hours, and a polymerization reaction was further carried out for 4.5 hours to obtain a peroxy bond-containing polymer. As a result of measuring the amount of residual monomer by GC, the polymerization conversion was 98% or more. Subsequently, 160 parts of MEK

[0136]

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A mixed solution of 086 parts was added dropwise over 30 minutes, and a polymerization reaction was further carried out at 70 ° C. for 3 hours and at 77 ° C. for 3 hours. As a result of GC analysis, the polymerization conversion rate of the monomer was 9
8% or more. (2) Introduction reaction of unsaturated group The polymer solution synthesized in the above (1) was diluted with MEK to adjust the concentration of the active ingredient to 30%. Next, pyridine was further added to 400 parts of the 30% solution in the same manner as in Example 2 to prepare a polymer solution, and the chlorine compound solution shown in Table 7 was added dropwise at 40 ° C. over 60 minutes. For 5 hours to introduce an unsaturated group. After the reaction, pyridine hydrochloride was removed by filtration, and the polymer solution was diluted twice with MEK and poured into a large excess of water or methanol while stirring to reprecipitate and purify the polymer.

GPC analysis of the sufficiently dried polymer powder in the same manner as in Example 1 showed that none of the polymers contained a low molecular weight compound. In addition, IR analysis showed that an unsaturated group had been introduced, and NMR analysis showed that all of the OH groups in the polymer had disappeared and that an unsaturated group had been newly introduced. 100 parts of each polymer powder was 400 parts of methanol,
Pour into a mixed solvent consisting of 1600 parts of toluene,
For 8 hours to extract a fluorine-free acrylic polymer (containing an unsaturated group) which is one of the by-product components.

Next, the remaining polymer was charged into 2000 parts of trichlorotrifluoroethane, and stirred at 40 ° C. for 24 hours to extract a fluoropolymer. The weight of the extract was measured to determine the constituent ratio of block copolymer / acrylic polymer not containing fluorine / fluorinated polymer in the powder. The weight ratio of the fluorine-containing polymer portion [structural unit (A)] and the fluorine-free polymer portion [structural unit (B)] in the block copolymer was calculated while checking the rate of introduction of unsaturated groups by NMR analysis. did.

Further, the block copolymer after the by-product extraction was dissolved and dispersed in deuterium-substituted acetone, and subjected to NMR analysis. Was determined.
The viscosity at 25 ° C. of a 30% by weight solution prepared by adding MEK to the block copolymer powder was measured. Table 7 shows the results. (Examples 18 and 19) In synthesizing a block copolymer, 80 parts of MMA, n-BMA70, H
Using 50 parts of EMA, MEK 371 was used during the second stage polymerization.
Parts, except that 200 parts of the mixed solution of
A block copolymer was synthesized under the same conditions as in Example 12.

Further, the reaction for introducing an unsaturated group and the purification and analysis of the block copolymer were carried out under the same conditions as in Examples 17 and 18. Table 7 shows the obtained results.

[0142]

[Table 7]

Note (1) in Table 7 has the same meaning as in Table 6 above. The chlorine compound has the following meaning. (1)

[0144]

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(2)

[0146]

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(3) Formula 90 (Comparative Example 1) In comparison with Example 5, the same block copolymer as in (2) of Example 1 was reacted with three compounds of an isocyanate compound and HEMA. , An unsaturated group introduction reaction was performed.

In the same reactor as in Example 5, 40 g of the block copolymer obtained by the same method as in (2) of Example 1 and DM
A mixed solution was prepared from 120 g of F, and 52 g of a burette of hexamethylene diisocyanate (Duranate 24A manufactured by Asahi Kasei Kogyo KK) and dibutyltin dilaurate 2 were prepared.
When 00 ppm was charged and the mixture was heated to 70 ° C. and reacted, after 3 hours, the polymer solution was in a gel state, and it was not possible to carry out the planned reaction with HEMA thereafter. (Comparative Example 2) In order to compare with Example 18, Example 18
And a block copolymer before introducing an unsaturated group, an isocyanate compound and 2-hydroxyethyl acrylate (H
The introduction reaction of the unsaturated group was carried out by the reaction of the three compounds EA).

The same reactor as in Comparative Example 1 was charged with 120 g of a 30% polymer solution prepared by diluting with MEK.
ppm, and the mixture was heated to 70 ° C. and reacted for 4 hours. Next, after the reaction solution was cooled to room temperature, HEA48 was used.
g and 50 ppm of hydroquinone dimethyl ether were added, and the mixture was heated to 65 ° C. and reacted for 4 hours. After completion of the reaction, the mixture was diluted to twice the volume with MEK and poured into a large excess of methanol with stirring to reprecipitate and purify the polymer.

MEK was added to the sufficiently dried polymer powder to prepare a 30% by weight solution. However, it was difficult to dissolve and disperse, and it took a longer time than in Example 18. 25
It was 7.2 poise when the viscosity at ℃ was measured. Comparative Example 3 For comparison with Example 13, ethylene glycol methacrylate monoester (Blenmer PE2
00), isobutyl methacrylate (IBMA) and a fluorinated monomer to give a random copolymer. Next, an unsaturated group-introducing reaction was carried out in the same manner as in Example 13 to obtain a fluorine-containing random copolymer containing an unsaturated group.

The random copolymer was charged with 181 parts of DMF in the same reactor as in Example 7, heated to 80 ° C. while blowing nitrogen gas, and 83 parts of Blemmer PE200, I
17 parts of BMA, 100 parts of Chemical Formula 65,

[0152]

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Was mixed with 2 parts of a mixed solution of 10 parts of DMF and 180 parts of DMF.
The solution was added dropwise over a period of time, and further reacted at the same temperature for 10 hours to obtain. The conversion of the monomer by GC analysis was 97% or more. The obtained polymer solution was diluted with DMF to obtain a 20% by weight solution. The introduction reaction of the unsaturated group was carried out under the same conditions and under the same conditions as in Example 13 (3). GPC analysis showed that no low molecular weight compound was contained, and IR analysis showed that unsaturated groups were introduced. In addition, NMR analysis revealed that about 70% of the OH groups of the polymer had disappeared, and that unsaturated had been introduced. The introduction rate was about 30% lower than that of Example 7. Also,
When a 30% by weight solution of DMF was prepared, the state of the solution was unstable, and the polymer was precipitated shortly after standing, so that the viscosity could not be measured. A stable polymer solution was obtained only after dilution with DMF to 10% by weight. (Examples 20 to 38, Comparative Examples 4 and 5) Examples 1 to 19,
The sensitivity of the fluoropolymer having an unsaturated group obtained in Comparative Examples 2 and 3 to UV was evaluated, and various tests were also conducted.

In each of the examples and comparative examples, 30
% Solution in a photopolymerization initiator (Darocur 117 manufactured by Merck)
3, a test solution was prepared by adding 4 parts of a sensitizer (indicated by a in Table 8) or a sensitizer (5-nitroacenaphthene, indicated by b in Table 8) to 100 parts of the polymer. Then, after coating on an aluminum plate (A1100 manufactured by Nippon Test Panel Co., Ltd. or a soft PVC film (DOP content: 50% by weight)) with a bar coater so that the dry film thickness becomes 10 μm, 120 is applied when the base material is aluminum. In the case of a soft PVC film, the film was heated and dried for 1 hour at 70 ° C. for 5 minutes to prepare a test plate, which was irradiated with a 2 kW high-pressure mercury lamp from a distance of 20 cm for a predetermined time.

The following evaluation was performed on the test plate after irradiation. 1) Solvent resistance In this test, it was determined whether UV curing had progressed. When the substrate was an aluminum plate, a immersion test was performed at room temperature for 24 hours using a film forming solvent at the time of coating the test plate. In the case of a PVC film, the surface was rubbed 20 times with a cotton cloth soaked with a solvent. The evaluation criteria are as follows.

A: No change in appearance. ：: The film swelled slightly but did not deteriorate. Δ: The film expanded and a part of the film was deteriorated. X: The film was dissolved. 2) Contact angle The contact angle between water and dodecane was measured, and the water / oil repellency of the surface was evaluated. 3) Adhesiveness 90 ° fold is applied to the substrate on which the coating film is formed.
The degree of peeling of the coating film after the repetition was evaluated.

A: No cracking of the film and no peeling. ：: The film was partially cracked but did not peel. Δ: Peeling was partially observed along the bent line. ×: Peeling was observed up to a position away from the bent line. Tables 8 and 9 show the irradiation time and the measurement results.

[0158]

[Table 8]

In Table 8, the photoinitiators and the like represent the following.
a: photoinitiator, Darocure 1173, b: sensitizer, 5-
Nitroacenaphthene

[0160]

[Table 9]

In Table 9, photoinitiators and the like are the same as in Table 8.
From this result, it was clarified that the fluorine-containing block copolymer having an unsaturated group of the present invention had undergone a curing reaction in response to UV. It was also found that the adhesion to the substrate and the water / oil repellency on the surface were extremely good. However, with respect to the water and oil repellency, Examples 12 and 1
3 shows a slightly lower value, indicating that it depends on the difference in the composition of the structural unit (A). Furthermore, when UV irradiation was not performed, good solubility in the solvent was exhibited, and a remarkable difference was observed as compared with the case where UV irradiation was performed, in which the coating film became insoluble.
From these results, it can be seen that it can be sufficiently applied as a resist material.

On the other hand, in the case of the polymer of Comparative Example 2, good adhesion was exhibited, but the surface had poor water / oil repellency as compared with the polymer of Example 18. Further, the sensitivity to UV also tended to be weaker than that of Example 18. In the test plate coated on aluminum, it was found that the difference in solubility of the film before and after UV irradiation in the solvent was not so large. Further, in the case of the random copolymer of Comparative Example 3, as compared with the polymer of Example 7, the adhesion to the base material was insufficient, and the responsiveness tended to be low. (Examples 39 to 44, Comparative Example 6) Examples 1, 3, 17,
The performance as a surface modifier of the polymer of No. 18, the polymer of Example 1 (2) and the polymer of Comparative Example 2 was evaluated.

The polymer powder was diluted with neopentyl glycol diacrylate so that the polymer concentration became 20%. 30 parts of epoxy acrylate (trade name SP-1506, manufactured by Showa Polymer Co., Ltd.) and urethane acrylate (trade name M-1100, manufactured by Toa Gosei Chemical Industry Co., Ltd.)
A solution composed of 30 parts, 35 parts of ethylene glycol diacrylate and 5 parts of benzoin isobutyl ether was prepared, and 10 parts of the 20% solution was added to 100 parts of the solution. Next, the aluminum plate used in Example 20 was applied using an applicator so that the film thickness became 35 μm.

This was irradiated with the same high-pressure mercury lamp as in Example 20 from a distance of 10 cm for 10 seconds to form a cured film. This cured film was immersed in acetone and 10% sulfuric acid for 48 hours, and the water and oil repellency of the surface before and after immersion was evaluated. Table 10 shows the results.

[0165]

[Table 10]

From these results, it was found that when the block copolymer of the present invention was added to the active energy ray-curable resin, water repellency and oil repellency, a function of fluorine, could be imparted to the surface. In particular, even after immersion in acetone, the water / oil repellency hardly decreases, and chemically bonds with the matrix polymer,
It was found that the durability of the modifying effect was very excellent.

In the case of the block copolymer having no unsaturated group, although there was no decrease in the performance after immersion in sulfuric acid, the water- and oil-repellency tended to decrease slightly after immersion in acetone. In addition, the polymer of Comparative Example 2 showed a tendency that the initial modifying effect was insufficient. (Examples 45 to 47) The performance of the polymers of Examples 35, 36 and 37 as a surface modifier was evaluated.

Urethane acrylate (trade name SP-1506, manufactured by Toa Gosei Chemical Industry Co., Ltd.) was dissolved in MEK to form a 30% solution, and a photopolymerization initiator (the above-mentioned Darocure-11) was dissolved.
73) was added 4 parts to 100 parts of the polymer to prepare a test solution. After adding 3 parts of each of the solutions prepared in Examples 35 to 37 to this solution, a film was formed on an aluminum plate and dried in the same manner as in Example 20 to prepare a test plate.

This test plate was irradiated with UV under the same conditions as in Example 14. Thereafter, the same 10% sulfuric acid aqueous solution immersion test as in Example 41 was performed. An adhesive tape having a width of 5 cm and manufactured by Sekisui Chemical Co., Ltd. was pressed back and forth on the cured film by reciprocating a 2 kg roller two times. After being left at 50 ° C. for 3 days in this state, the tape was peeled off, and the tape surface was subjected to ESCA analysis (analysis using an X-ray photoelectron analyzer) to evaluate whether or not the fluorine component had been transferred. Table 11 shows the results.

[0170]

[Table 11]

As a result, it was found that the surface performance was not deteriorated even by immersion in the sulfuric acid aqueous solution, and that no fluorine component was transferred to the adherend. (Examples 48 to 50) The performance of the polymer used in Examples 21, 23, and 25 when a solution was used as a resist material was evaluated. The performance when each polymer solution was used as a resist material was evaluated. Each polymer solution was applied on an aluminum plate so that the film thickness after drying was 1 μm, and was heated and dried at 100 ° C. for 10 minutes. A negative for lithographic printing was press-bonded to this and UV-irradiated with a 2 kW high-pressure mercury lamp from a distance of 20 cm for 10 seconds. Then remove the negative,
The test plate was immersed in acetone and developed to prepare a test plate for dry lithographic printing. Printing was performed using this test plate, and performance was evaluated. Table 12 shows the results.

[0172]

[Table 12]

As a result, excellent printability was exhibited, indicating that the present invention is also useful as a resist material.

[0174]

As described above in detail, according to the first aspect, the miscibility with other resins, adhesion to substrates, and active energy rays based on the structural unit (B) in the block copolymer. Characteristics such as sensitivity are fully exhibited. In addition, there is an effect that characteristics based on fluorine such as water repellency and oil repellency are effectively exhibited based on the structural unit (A).

According to the second aspect, even when the structural unit (A) contains a predetermined amount of a vinyl monomer containing no fluorine, the effect of the first aspect can be effectively exhibited. To play. According to the third invention, a dehydrochlorination reaction is performed by reacting a block copolymer containing a hydroxyl group with a chlorine compound containing an unsaturated group, whereby the reaction of the first invention or the second invention is performed. This has the effect that the block copolymer can be reliably obtained.

According to the fourth invention, by reacting a chlorine-containing block copolymer with a hydroxyl-containing compound having an unsaturated group, a dehydrochlorination reaction is carried out, whereby the first invention or the second invention is carried out. The effect is obtained that the block copolymer of the invention of the invention is surely obtained. According to the fifth invention, the active energy ray-curable material comprising the block copolymer of the first invention or the second invention can be cured in response to the active energy ray, so that the resist material or the active energy ray-curable This has the effect of being useful as a surface modifier for polymer materials.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-210613 (JP, A) JP-A-60-22410 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 293/00 C08F 299/00 C08L 53/00

Claims (5)

(57) [Claims] 1. A polymer part derived from the following formula 1.
Become the structural unit (A), it becomes from the following formula 11 polymer portion and the structural unit comprising the following chemical formula 35 or of 47 from polymer portion to units derived from (B), the structural units (A) / The ratio of the structural unit (B) is 80/20 by weight.
10/90, wherein the viscosity of the solution adjusted to 30% by weight by dissolving or dispersing in a non-fluorinated organic solvent which is a good solvent for the structural unit (B) is 0.05 to 7 poise at 25 ° C. A fluorine-containing block copolymer containing a characteristic unsaturated group. ## STR1 ## CH ₂ = CR in ₁ COOR ₂ Rf formulas, R ₁ a hydrogen atom or a methyl group, R ₂ is ## STR2 ## is -C _P H _2P, embedded image -C (C _P H _{2P + 1} ) H-, embedded image or —CH ₂ C (C _P H _{2P + 1} ) H or —CH ₂ C
H ₂ O-, Rf is embedded image -C _n F _{2n + 1,} embedded image - (CF _{2) n} H, embedded image _{- (CF 2) P OC m} H 2m CiF 2i + 1, embedded image _{- (CF 2) P OC m} H 2m CiF 2i H, embedded image , It is. However, p is 1 to 10, n is 1 to 16, m is 0 to
10, i is an integer of 0 to 16. CH ₂ ＣＲCR ₃ R ₄ wherein R ₃ is a hydrogen atom or a methyl group or —CH ₂ COOH, and R ₄ is —COOR ₅ (where R ₅ is hydrogen Atom, , , , ## STR17 ## -CH ₂ CH ₂ N (C _s H _{2s + 1} ) ₂ , , Embedded image -CH ₂ CH = CH _2, a straight-chain or branched embedded image -C _n H _{2n + 1,} embedded image of the straight-chain or branched -C _P H _{2P + 1} OH, ## STR22 ## --CH ₂ CH (OH) CH ₃ , ## STR23 ##-(C ₂ H ₄ O) _r C _s H _{2s + 1} , ## _STR24 ##-[CH ₂ CH (CH ₃ ) O _R C _s H _{2s +1} . However, p is 1 to 10, n is 1 to 16, r is 2 to
20, s is an integer of 0 to 8. ) Embedded image -CONR ₆ R ₇ (wherein, R ₆ a hydrogen atom or an embedded image is _{-C P H 2P + 1, R} 7 is a hydrogen atom, embedded image of the linear or branched - C _P H _{2P + 1} or —CH ₂ OH, where p is an integer of 1 to 10.) , Embedded image -CONHC (CH ₃ ) ₂ CH ₂ COCH ₃ , embedded image -CONHC (CH ₃ ) ₂ CH ₂ SO ₃ H, embedded image , Embedded image —CN or —OCOC _n H _{2n + 1} (in the formula, n is an integer of 1 to 16, and may be linear or branched). In the formula, R ₈ is a hydrogen atom or a methyl group, R ₉ is —C ₂ H ₄ O— or —CH ₂ CH (CH ₃ ) O—, and R ₁₀ is , , Embedded image CH ₂ = CH-, embedded image _{CH 2 = C (CH 3)} -, embedded image _{CH 2 = CH-COO-C} 2 H 4 O-, embedded image CH ₂ = _{C (CH 3) COO-C} 2 H 4 O
−, , Or It is. Here, t is an integer of 1 to 20. Embedded image In the formula, R ₁₁ is a hydrogen atom or a methyl group, and R ₁₂ is , , , , Embedded image where —CH ₂ CH ₂ OCOCH ＝ CH ₂ . 2. The composition according to claim 1, wherein the structural unit (A) comprises at least 40% by weight of a polymer portion derived from Chemical Formula 1 and at most 60% by weight of a polymer portion derived from Chemical Formula 11. A fluorinated block copolymer containing the unsaturated group as described above. 3. A structural unit (A) derived from the above chemical formula 1.
And a polymer moiety derived from the above formula (11) and
Structural unit (B ₁ ) consisting of a polymer moiety derived from 3
Or a structural unit (A) comprising 40% by weight or more of a polymer portion derived from the above formula 1 and 60% by weight or less of a polymer portion derived from the above formula 11; Reacting a fluorine-containing block copolymer consisting of a structural unit (B ₁ ) consisting of a polymer part derived from 11 and a polymer part derived from the following formula 53 with a compound represented by the following formula 54; The method for producing a fluorine-containing block copolymer containing an unsaturated group according to claim 1 or 2, wherein the fluorine-containing block copolymer containing an unsaturated group is produced based on a dehydrochlorination reaction. CH ₂ ＣＲCR ₈ —COO (R ₉ ) _t H wherein R ₈ is a hydrogen atom or a methyl group, and R ₉ is
Or Formula 37. Here, t is an integer of 1 to 20. R ₁₀ -COCl In the formula, R ₁₀ is the above-mentioned chemical formula 38, chemical formula 39, chemical formula 40, chemical formula 41, chemical formula 42 or chemical formula 43. 4. From a polymer moiety derived from the above chemical formula 1.
A fluorine-containing block copolymer consisting of a structural unit (A), a structural unit (B ₂ ) composed of a polymer part derived from the above chemical formula 11, and a polymer part derived from the following chemical formula 55; 40% by weight of polymer part derived from
From the structural unit (A) comprising the above and a polymer portion derived from the chemical formula 11 and 60% by weight or less, and the polymer unit derived from the chemical formula 11 and the structural unit (B ₂ ) derived from the following chemical formula 55 A fluorinated block copolymer containing an unsaturated group is produced based on a dehydrochlorination reaction by reacting the fluorinated block copolymer with a compound represented by the following formula: 3. A method for producing a fluorine-containing block copolymer containing an unsaturated group according to 1 or 2. Embedded image R ₁₃ -COCl wherein, R ₁₃ embedded image is CH ₂ = CH-, embedded image _{CH 2 = C (CH 3)} -, embedded image CH ₂ = CH-COO-C ₂ H ₄ − or CH ₂ ＣC (CH ₃ ) COO—C ₂ H ₄ −. R ₁₂ OH In the formula, R ₁₂ is the aforementioned formula (48), (49), (50), (51) or (52). 5. An active energy ray curing material comprising the block copolymer according to claim 1 and curable by an active energy ray.