JP3084690B2 - Method for producing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a (meth) acrylate polymer. More specifically, it is suitably used as an adhesive which gives a pressure-sensitive adhesive layer or a pressure-sensitive adhesive layer by polymerization or cross-linking reaction upon irradiation, or which functions as an adhesive for laminating (meth). The present invention relates to a method for producing an acrylate polymer.

[0002]

2. Description of the Related Art (Meth) acrylic acid is used as an adhesive for forming an adhesive layer by applying directly or on a release material thereof onto a substrate such as a tape, a film, a sheet or the like, and drying by heating. G polymer is widely used. Also, the adhesive used when manufacturing a laminated product by laminating paper and a plastic film, paper and a metal foil, plastic film and a metal foil, etc. is mainly composed of a (meth) acrylate polymer. Many compositions are used.

[0003] Such (meth) acrylate polymers are:
Conventionally, it has been produced by solution polymerization using various organic solvents as a solvent or emulsion polymerization in which a monomer component is polymerized in a state of being emulsified with water. However, in the case of solution polymerization using an organic solvent, a process for producing an adhesive or an adhesive for laminating or a final product such as an adhesive tape, an adhesive film, an adhesive sheet, or a laminating agent.
In any one of the processes of manufacturing a product, etc., it is indispensable to dry and remove the used organic solvent, and this drying and removing process requires large equipment and a large amount of energy. In addition, a great deal of equipment is required to reduce the environmental problems and the danger of ignition of organic solvents. On the other hand, in emulsion polymerization, equipment for environmental problems and danger of ignition is not required as much as in the case of solution polymerization, but drying and removal of water are indispensable, and the equipment or energy consumption for this is larger than in the case of solution polymerization. It can be.

In order to solve these problems, a method has been proposed in which a (meth) acrylate monomer is polymerized without a solvent to obtain a desired polymer. JP-A-58-87171 proposes a method in which the reaction is divided into two stages by changing the polymerization temperature to polymerize the polymer without solvent. Also, Japanese Patent Application Laid-Open No. Sho 58-1686
No. 10 proposes a method of polymerizing a polymer without a solvent by sequentially increasing the temperature using a special reactor.

However, in the solventless polymerization method, since the obtained polymer does not show fluidity at around normal temperature, the polymer must be taken out of the reaction vessel unless the temperature is set to 100 to 150 ° C. or higher, or any post-treatment performed thereafter. ,
For example, it has a drawback that filtration or compounding of additives is difficult and workability is extremely poor. Further, keeping the polymer at such a high temperature is not preferable because it causes deterioration and coloring of the polymer. Further, when the (meth) acrylate monomer is polymerized without a solvent, it is also difficult to control the molecular weight and molecular weight distribution of the polymer arbitrarily.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a (meth) acrylate polymer.

Another object of the present invention is to solve the above-mentioned problems when polymerizing a (meth) acrylate monomer without the need for drying and removing the solvent and without using a solvent. To provide a method for producing a polymer.

Still another object of the present invention is to provide a method for producing a (meth) acrylate polymer which can be suitably used for a radiation-curable pressure-sensitive adhesive or a laminating adhesive.

Further objects and advantages of the present invention will become apparent from the description hereinafter.

[0010]

According to the present invention, the above objects and advantages of the present invention can be achieved by the following general formula (1):

[0011]

Embedded image

At least one kind of (meth) acrylate represented by the formula (1) and a radical reactivity different from each other in the molecule:
At least one of the compounds having two carbon-carbon unsaturated bonds
A mixture of one type of radically polymerizable compound is subjected to radical polymerization in the presence of an alkyl vinyl ether having an alkyl group having 2 to 18 carbon atoms as a polymerization solvent.
Use gel permeation chromatography for 2-4 pipes.
Shows the molecular weight distribution with a peak and the minimum peak of the molecular weight is
Polymerization showing polystyrene equivalent molecular weight of 83,000 or more
Is achieved by the polymer manufacturing process according to Rukoto characterized yielding body.

In the above formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alkyl group having 1 to 15 carbon atoms. Alkyl group R ² may be linear, branched or cyclic.

As the (meth) acrylate represented by the general formula (1), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Acrylate, pentyl (meta)
Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate
And nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, neopentyl (meth) acrylate, and ethylhexyl (meth) acrylate. Of these, propyl acrylate, butyl acrylate, pentyl acrylate and hexyl acrylate are preferably used.
DOO, heptyl acrylate Le - DOO, octyl acrylate Le - DOO, Noniruakurire - DOO, Deshiruakurire - DOO, ethylhexyl acrylate Le - number of carbon atoms of the R ^2, such bets are 3-10 alkyl acrylate Le - is DOO.

In the present invention, these (meth) acrylates represented by the general formula (1) can be used alone or in combination of two or more. Take (meta)
The acrylate is particularly preferably in a mixture of other radically polymerizable compounds [(meth) acrylate and other radically polymerizable compounds] excluding the alkyl vinyl ether.
70 to 99.9% by weight (hereinafter simply indicated as%)
I have.

The carbon number of 2 to 18 used in the present invention is
Examples of the alkyl vinyl ether having an alkyl group include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, decyl vinyl ether, and pendadecyl. Chain (including branched) alkyl vinyl ethers such as vinyl ether and octadecyl vinyl ether ; cyclic alkyl vinyl such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and cyclooctyl vinyl ether Ether ; 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether
Examples thereof include hydroxyl group-containing alkyl vinyl ethers such as ter. Among these, those that are preferably used are:
Decyl vinyl ether, pentadecyl vinyl ether,
It is a chain (including branched) alkyl vinyl ether having 8 to 18 carbon atoms such as octadecyl vinyl ether. These alkyl vinyl ethers can be used alone or in combination of two or more.

In the present invention, the alkyl vinyl ether is preferably used in an amount of 1 to 100 parts by weight of the mixture of the radical polymerizable compound excluding the alkyl vinyl ether.
It is used in a proportion of 0 to 1000 parts by weight, more preferably 30 to 500 parts by weight, particularly preferably 70 to 200 parts by weight.

In the present invention, other radically polymerizable compounds which can be used as the (meth) acrylate represented by the general formula (1) and the alkyl vinyl ether having an alkyl group having 2 to 18 carbon atoms. For example,

(A): unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and crotonic acid; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Alkyl (meth) acrylates having a hydroxyl group such as acrylate; vinyl alcohol, allyl alcohol
Unsaturated alcohols such as thiol; the following general formula (2)

[0020]

Embedded image

(Meth) acrylates having an amino group represented by the following formula: for example, N, N-dimethylaminoethyl (meth) acrylate;
N, N-diethylaminoethyl (meth) acrylate,
N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and the like;

(B): halogenated unsaturated hydrocarbons, for example, vinyl chloride, vinylidene chloride, isopropenyl chloride, isobutenyl chloride, chloroprene, α-chlorostyrene, β-chlorostyrene, α-bromostyrene, β-
Bromostyrene, α-iodostyrene, β-iodostyrene and the like; or unsaturated fatty acid haloalkyl esters,
For example, 2-chloroethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate,
3-bromo-2-hydroxypropyl (meth) acrylate and the like;

(C): a compound having two carbon-carbon unsaturated bonds having different radical reactivities in a molecule, specifically, the following general formula (3)

[0024]

Embedded image

A compound represented by the following general formula (4)

[0026]

Embedded image

A compound represented by the following general formula (5)

[0028]

Embedded image

A compound represented by the following general formula (6)

[0030]

Embedded image

A compound represented by the following general formula (7)

[0032]

Embedded image

A compound represented by the following general formula (8):

[0034]

Embedded image

A compound represented by the formula:

(D): vinyl compounds having a cyano group such as acrylonitrile, cyanoethyl (meth) acrylate, cyanopropyl (meth) acrylate, etc .; acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N , N- dibutyl acrylamide, vinyl compounds <br/> compound having a diacetone acrylamide amide groups; N- vinylpyrrolidone, N- N-vinyl lactams such as vinylcaprolactam; vinyl acetate; styrene; and α- methylstyrene Can be mentioned.

Among these other radically polymerizable compounds, the compound represented by (C) is an essential component. The compounds shown in (A) and (D) are particularly useful for adjusting the adhesive property or adhesive property to a desired one when the polymer is compounded as an adhesive or an adhesive for lamination. , (B) and (C) are particularly useful for increasing the reactivity of the polymer to radiation. In addition, using the indicated compound (C), the molecular weight distribution of the polymer can be broadened <br/> Ru Oh. The present invention using the compound represented by (C)
When the polymer is analyzed by gel permeation chromatography, a molecular weight distribution having 2 to 4 peaks can be observed. Also, those peaks
The minimum peak of the molecular weight is 83,000 or more.
Shows the molecular weight in terms of styrene.

In the present invention, the other radically polymerizable compounds shown in the above (A) to (D) can be used alone or in combination of two or more, depending on the desired use, except for the alkyl vinyl ether. in a mixture of other radically polymerizable compound, good Mashiku are included from 0.1 to 30%.

The polymerization reaction system in the present invention may be a continuous reaction or a batch reaction. Further, a batch charge method or an increment charge
It is also possible to adopt a system. The polymerization temperature is usually from 10 to 180 ° C, particularly preferably from 50 to 120 ° C.

The polymerization initiator used in the polymerization may be a conventional thermal radical initiator such as peroxydica.
Bones, ketone peroxides, peroxykitters
Organic peroxides such as toluene, hydroperoxide, dialkyl peroxide, diacyl peroxide and peroxyester; 2,2′-azobisisobutyronitrile;
2,2'-azobis (2-methylbutyronitrile), 2,2
2'-azobis (2,4-dimethylvaleronitrile),
Azo compounds such as dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (cyclohexane-1-carbonitrile) can be used. The amount of the polymerization initiator to be used is preferably 0.0001 to 5 parts by weight, particularly preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the mixture of the other radically polymerizable compounds excluding the alkyl vinyl ether. Parts by weight.

In the polymerization, a chain transfer agent may be used. Examples of the chain transfer agent include alkyl mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan and dodecyl mercaptan; octyl thioglycolate, nonyl thioglycolate, 2-ethylhexyl thioglycolate, β-mercaptopropionic acid 2 Thioglycolic acid esters such as -ethylhexyl and pentaerythritol tetrathioglycolate; 2,4-diphenyl-4-methyl-1-pentene, 1-methyl-4-isopropylidene-1-cyclohexene and the like Can be mentioned. Of these, thioglycolic acid esters; 2,4-diphenyl-4-
When methyl-1-pentene, 1-methyl-4-isopropylidene-1-cyclohexene, or the like is used, the polymerization product has a low odor, which is preferable. The amount of the chain transfer agent to be used is preferably 0.1 to 100 parts by weight of the mixture of the other radically polymerizable compounds except the alkyl vinyl ether.
001 to 3 parts by weight.

In the mixture containing the polymer obtained by the method of the present invention (hereinafter referred to as "reaction mixture"), unreacted alkyl vinyl ether remains. The unreacted alkyl vinyl ether reacts when irradiated with a composition (hereinafter abbreviated as “composition”) containing the reaction mixture as a pressure-sensitive adhesive or an adhesive for laminating, For curing or crosslinking, it is necessary not to remove unreacted alkyl vinyl ether.

The amount of the unreacted alkyl vinyl ether can be controlled by the polymerization conditions. However, in consideration of the workability in treating the polymer or the reactivity in the case of irradiation, the reaction is usually carried out. When the concentration of the polymer in the mixture is 6
It should be controlled to be 0-95%, preferably 80-90%.

When formulating the composition, radiation-reactive diluents are usually used for the purpose of controlling the viscosity of the composition, obtaining desired viscosity / adhesive properties, or enhancing the reactivity upon irradiation. Various additives such as an agent, a crosslinking agent and a (radiation) polymerization initiator can be blended. The following compounds can be exemplified as examples of such various additives.

Radiation-reactive diluent: The radiation-reactive diluent is used in order to reduce the viscosity of the composition, and is preferably 3 to 50%, more preferably 10 to 40% in the composition. It is blended in a ratio. Examples of such a radiation-reactive diluent include compounds having a carbon-carbon unsaturated bond.

Specifically, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth)
Acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate
3-chloro-2-hydroxypropyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol -(Meth) acrylate, methyltriethylenediglycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acryloylmorpholine, the general formula (Meth) acrylic compound represented by the formula (1)
, Isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, the following general formula (9)

[0047]

Embedded image

Monofunctional (meth) acrylic represented by
G, the following general formula (10)

[0049]

Embedded image

Monofunctional (meth) acrylic represented by
G, the following general formula (11)

[0051]

Embedded image

Monofunctional (meth) acrylic acid represented by
G, the following general formula (12)

[0053]

Embedded image

Monofunctional (meth) acrylic represented by the formula
And the following general formula (13)

[0055]

Embedded image

N-vinyllactams represented by the following formulas can be exemplified.

Cross-linking agent: The cross-linking agent is compounded for accelerating the curing of the composition by irradiation with radiation, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate. , Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Acrylate - DOO, 1,4 butanediol - distearate (meth) acrylate - DOO, 1,6 hexanediol - distearate (meth) acrylate - DOO, neopentyl glycolate - Le di (meth) acrylate -
G, trimethylolpropane trioxyethyl (meth)
Acrylate, tricyclodecanedimethanol di (meth) acrylate, dicyclopentadienedi (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2- (Hydroxyethyl) isocyanurate di (meth) acrylate
Polyfunctional (meth) acrylates such as epoxy (meth) acrylate in which (meth) acrylate is added to diglycidyl ether of bisphenol A, 3-acryloyloxyglycerin monomethacrylate, and bisphenol A Examples can be given. The amount of these crosslinking agents is 15
%, Particularly preferably 10% or less. If it exceeds 15%, upon curing by irradiation with radiation, crosslinking proceeds excessively, and the pressure-sensitive adhesive layer or the adhesive layer becomes hard, and it tends to be difficult to obtain desired adhesive strength, adhesive strength, and the like.

(Radiation) Polymerization initiator: When the radiation to be irradiated to polymerize or crosslink the composition is a high energy ray such as an electron beam or γ-ray,
Usually, it is not necessary to mix a polymerization initiator, but in the case of low energy rays such as ultraviolet rays and visible light, it is necessary to mix a radiation polymerization initiator. Examples of such a radiation polymerization initiator include benzophenone, benzoin, benzoin isobutyl ether, benzyl, and benzoin ethyl ether.
Ter, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, 4-chlorobenzophenone, triphenylamine, carbazole, 3-methylacetophenone, 4,4'-dimethoxybenzophenone,
4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether, acetophenone diethylketal, benzoinethyl ether, 1-hydroxycyclohexyl phenyl ketone, 4'-isopropyl-2
-Hydroxy-2-methyl-propiophenone, 2-hydroxy-2-methyl-propiophenone, α, α′-dichloro-4-phenoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, chloro Thioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, 3,3-dimethyl-4-
Methoxybenzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, α
-Hydroxycyclohexyl phenyl ketone, Uvecryl P36 (high molecular weight benzophenone manufactured by UCB),
Radical polymerization initiators such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide; 2,5-diethoxy-4-(p-tolyl-mercapto) benzene diazonium PF ₆ ^-, 2,4,6-trichlorobenzene diazonium
PF ₆ ^-, 4-dimethylamino-naphthalene diazonium P
F ₆ ^-, cyclopentadienyl ferrocenium PF ₆ ^- ion polymerization initiators such as and the like. These polymerization initiators are usually 0.5 to 20%, preferably 3 to 1% in the total composition.
0% can be blended.

If necessary, a radiosensitizer may be used. Examples of such a radiosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate,
Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, Ubecryl P102, UCB
03, 104, 105 and the like. These radiosensitizers are usually contained in the composition in an amount of 15% or less, preferably 10% or less.
The following can be blended.

Note that high energy such as electron beam and γ-ray
It is needless to say that the radiation polymerization initiator as described above can be blended even in the case of irradiating a ray. Particularly, when the ionic polymerization initiator is blended, the degree of curing can be increased.

Further, in place of the radiation polymerization initiator as described above, an ordinary thermal polymerization initiator can be blended. In such a case, in addition to the polymerization or crosslinking of the composition by irradiation with radiation, the polymerization or crosslinking of the composition by heat can be performed. Examples of such a thermal polymerization initiator include, for example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, and 2,2 ′. -Azobisisobutyronitrile,
2,2'-azobis (2-methylbutyronitrile), 2,2
2'-azobis (2,4-dimethylvaleronitrile),
Examples thereof include dimethyl 2,2'-azobisbutyrate and 1,1'-azobis (cyclohexane-1-carbonitrile).

Other additives: Further, the composition may contain a tackifier such as a rosin resin, a terpene-phenol resin, a terpene resin, a xylene resin, a chain transfer agent, an antioxidant, and an antiaging agent. Agents, UV absorbers, thermal polymerization inhibitors,
Coupling agents, fillers, pigments, dyes, and the like can be added as necessary.

[0063]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1200 g of 2-ethylhexyl acrylate, 120 g of methyl methacrylate, 90 g of acrylic acid, 45 g of 3-chloro-2-hydroxypropyl methacrylate,
45 g of dicyclopentenyloxyethyl acrylate,
7.5 g of dodecyl mercaptan and 600 g of lauryl vinyl ether were placed in a reaction vessel, and after sufficiently purging with nitrogen, 12 g of benzoyl peroxide was added and reacted at 90 ° C. for 12 hours with stirring.

After completion of the reaction, about 1 g of the reaction mixture was dissolved in about 30 g of tetrahydrofuran, and this monomer was analyzed by gas chromatography to obtain each monomer.
And the conversion of lauryl vinyl ether were determined. The following equation (1)

[0066]

(Equation 1)

The reaction rates determined based on the above were 55% for lauryl vinyl ether and 99% or more for all others.

When the reaction mixture was analyzed by gel permeation chromatography, a chromatogram having three overlapping peaks was observed in the high molecular weight region. The molecular weights of the tops of these three peaks were 83,000, 251,000, and 581,000 in terms of polystyrene. The composition ratios by molecular weight are as follows: those exceeding 400,000 in terms of polystyrene are 27.5%;
3.3% and less than 100,000 were 39.2%.

Further, the viscosity of the reaction mixture at 90 ° C. was measured with a Brookfield viscometer.
It was 2,000 CPS.

Example 2 1215 g of 2-ethylhexyl acrylate, 90 g of vinyl acetate acetate, 90 g of acrylic acid, 45 g of 3-chloro-2-hydroxypropyl methacrylate, 45 g of dicyclopentenyloxyethyl acrylate, 15 g of N-vinylpyrrolidone, 7.5 g of dodecyl mercaptan and 600 g of lauryl vinyl ether were placed in a reaction vessel, and sufficiently purged with nitrogen.
2 g was added and reacted at 90 ° C. for 12 hours with stirring.

After completion of the reaction, the reaction mixture was analyzed in the same manner as in Example 1, and the conversion of each monomer and lauryl vinyl ether was determined.
Tell was 58% and all others were over 99%.

When the reaction mixture was analyzed by gel permeation chromatography, a chromatogram having three overlapping peaks was observed in the high molecular weight region. The molecular weights at the top of these three peaks were 91,000, 263,000, and 61,000, in terms of polystyrene. The composition ratios by molecular weight are as follows: polystyrene conversion of more than 400,000, 29.1%;
5.1% and less than 100,000 were 35.8%.

Further, the viscosity of the reaction mixture at 90 ° C. was measured with a Brookfield viscometer.
It was 3,000 CPS.

Reference Example 1 To 77.1 g of the reaction mixture of Example 1, 8.9 g of 2-hydroxyethyl acrylate and phenoxyethyl acrylate were added.
And 6 g of isobornyl acrylate and 3 g of tripropylene glycol diacrylate were mixed to obtain a composition.

The obtained composition was coated on a 50 μm-thick polyester film so as to be 25 g / m ² ,
Thereafter, the coated surface was cured by irradiating an electron beam of 3 Mrad at an acceleration voltage of 165 KV. The irradiation of the electron beam
The test was performed under a nitrogen atmosphere using a ten-type electron beam accelerator (manufactured by Energy Sciences Inc.).

After the curing was completed, the polyester film coated with the composition was cut into a tape having a width of 25 mm.
It was crimped on a stainless steel plate polished by the method described in Z0237 using a manual roller described in JISZ0237. This was allowed to stand at a temperature of 25 ° C. for 40 minutes and then at a temperature of 25 ° C. at a pulling speed of 50 mm / min.
When a peel test was conducted, a peel force of 1300 g was shown.

Reference Example 2 8.1 g of 2-hydroxyethyl acrylate and phenoxyethyl acrylate were added to 77.9 g of the reaction mixture of Example 2.
And 6 g of isobornyl acrylate and 3 g of tripropylene glycol diacrylate were mixed to obtain a composition.

The obtained composition was applied to a polyester film having a thickness of 50 μm and cured in the same manner as in Example 1 to prepare a test piece, and a 180 ° peel test was conducted.
The peel force was 1600 g.

[0079]

According to the method of the present invention, it such ku using any special apparatus at relatively low temperatures, the polymer can be a manufacturing and polymer molecular weight distribution, etc. Control of Easy. Further, the reaction mixture of the polymer obtained by the method of the present invention, because its viscosity is not high,
The workability in the post-treatment after the production is also superior to the conventional polymer produced without a solvent. Furthermore, the low molecular weight compound contained in the reaction mixture of the polymer obtained by the method of the present invention, by irradiating radiation after coating,
Alternatively, it does not need to be removed because it reacts to polymerize or crosslink by heating.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Katsushi Igarashi 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-51-132233 (JP, A) JP-A Sho 60-1006813 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 2/00-2/08

Claims (1)

(57) [Claims] [Claim 1] The following general formula (1) Oyo least one in represented by (meth) acrylate
And carbon-carbon radicals having different radical reactivity in the molecule.
A mixture of radically polymerizable compounds containing at least one compound having two saturated bonds is subjected to radical polymerization in the presence of an alkyl vinyl ether having an alkyl group having 2 to 18 carbon atoms as a polymerization solvent, and gel permeation is performed.
Fraction with 2 to 4 peaks
Shows a molecular weight distribution and the minimum peak of the molecular weight is 83,000.
A polymer having the above polystyrene equivalent molecular weight is produced.
Preparation of a polymer with fit Rukoto features.