JPS6119606A - Production of actinic energy ray-curable silicone graft polymer - Google Patents

Abstract

PURPOSE:To produce the titled graft polymer which can give a cured product excellent in water repellency, water resistance, mechanical strength, etc., by radical-polymerizing a radical-polymerizable silicone macromonomer with a specified compound. CONSTITUTION:A living polymer obtained by anion-polymerizing a cyclic siloxane of formula I (wherein R1 is methyl, ethyl or phenyl and p is 3 or 4) is reacted with a radical-polymerizable silicone compound of formula II or III(wherein R2 is H or methyl, m is 0 or 1, R3-4 are each methyl, ethyl, or phenyl, n is 1-3, and l is 0-2 when n=0, or 2 when m=1) to obtain a radical- polymerizable silicone macromonomer. 1-90wt% this macromonomer is radical- polymerized with 1-95wt% compound having a radical-polymerizable functional group and another actinic energy ray-reactive functional group (e.g., an ester of acrylic acid with hydroxychalcone of formula IV).

Description

Detailed Description of the Invention (1) Purpose of the Invention [Field of Industrial Application] The present invention is directed to the field of seed pills in which silicone is currently used;
For example, active energy ray-curable silicone graft polymers that can be used as raw materials and surface modifiers for coating agents, sealants, potting agents, mold release agents, various plastic films and molded products, fibers, rubber, paints, adhesives, etc. The present invention relates to a manufacturing method.

[Conventional technology]

Conventionally, several methods have been proposed for producing silicone-based graft polymers, such as Japanese Patent Publication No. 32-68
9S, Japanese Patent Publication No. 47-16199, etc., an active group is formed by abstracting hydrogen from a lower alkyl group bonded to a silicon atom of silicone, and an organic polymer is grafted thereto (hereinafter referred to as silicone). As shown in Japanese Patent Publication No. 46.9355, Japanese Patent Application Laid-Open No. 52-135391, etc., a silicone having an active group is prepared in advance, and an organic polymer i is grafted onto the active group. method (hereinafter abbreviated as method using silicone with active group) and Japanese Patent Publication No. 1983-
There is a method of radical copolymerization of a radically polymerizable silicone macromonomer and a radically polymerizable monomer, as disclosed in Japanese Patent Application No. 78256, Japanese Patent Application No. 58-1120, and Japanese Patent Application Laid-open No. 167606/1984.

Among these proposed methods for producing silicone-based graft polymers, in the silicone hydrogen abstraction method, hydrogen abstraction from a lower alkyl group bonded to a silicon atom is an essential condition for producing a graft polymer. Process 1 conditions suitable for hydrogen abstraction from a lower alkyl group bonded to a silicon atom button are required. A commonly used method is to cause a heating reaction between silicone, a monomer capable of forming the polymer to be grafted onto the silicone, and an organic peroxide. Conditions such as type, amount, and reaction temperature must be carefully selected. For example, for catalyst trapping, azo-based initiators such as azobisisobutyronitrile cannot normally be used because silicone has a low hydrogen abstraction ability, resulting in low grafting efficiency. Generally, peroxides represented by ROOH or ROOR (R is an organic group) are used, such as benzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide,
Examples include cumene hydroperoxide, but among these peroxides, the ease with which the water index can be extracted from silicone varies depending on the type of peroxide. In addition, although the reaction temperature is above the decomposition temperature of the organic peroxide used, the ease with which hydrogen can be abstracted from silicone is affected by the temperature, and the molecular weight of the organic polymer to be grafted is also affected by the temperature. However, it is difficult to control the influence of 5, and furthermore, the crosslinking reaction progresses and gelation tends to occur during the reaction, making it impossible to obtain a graft polymer with a clear monostructure. That is, the molecular weight and number of organic polymers grafted per silicone molecule are different, and there is also a possibility that unreacted silicone that is not grafted is included.

In addition, when a method using silicone having an active group is busy, for example, according to the method disclosed in Japanese Patent Publication No. 46-9555, a silicone having an active group is reacted with a living polymer obtained by anionic polymerization. Although a silicone-based graft polymer can be obtained by using this method, the production cost is high due to the troublesome production process using anionic polymerization and the need to select monomers that are resistant to anionic polymerization, which is by no means satisfactory. Also, JP-A-5
According to the method disclosed in 2-1!15391, a polysiloxane polyester containing maleic acid in the main chain is synthesized, and an electron-donating monomer that easily forms a charge transfer complex with maleic acid is mixed therein. Silicone-based graft polymers can be obtained by graft polymerization, but there are restrictions on the monomers that can be used, and gels may form in some cases.

On the other hand, in the method of radical copolymerization of a radically polymerizable silicone macromonomer and a radically polymerizable monomer, the mixing ratio of the silicone macromonomer and the radically polymerizable monomer can be freely changed, and the radically polymerizable monomer with functions can be used. Silicone-based graft polymers with a clear structure, functionality, and controlled molecular weight have been developed for reasons such as the ability to use radically polymerizable monomers with reactive groups, and the ability to use normal radical polymerization operations. It can be produced industrially with great advantage.

[Problem that the invention seeks to solve]

As mentioned above, among the methods for producing silicone-based graft polymers, the hydrogen abstraction method of silicone and the method using silicone with active groups are: (1) Gel tends to occur in the production of silicone-based graft polymers; (2) The polymer to be grafted onto silicone. There is a limit to the monomers that can form a silicone-based graft polymer. Even if you prepare a silicone-based graft polymer in advance, react the silicone-based graft polymer with an active energy-curable functional group-containing compound, and introduce the functional group. However, there are problems in that it is difficult to provide the silicone-based graft polymer with reactive sites. On the other hand, the conventional method for producing silicone graft polymers by radical copolymerization of radically polymerizable silicone macromonomers and radically polymerizable monomers does not have the above-mentioned difficulties, but active energy ray-curable silicone graft polymers There were no examples of polymer production.

(2) Structure of the Invention [Means for Solving the Problems] Conventionally, no method for producing active energy ray-curable silicone graft polymers has been found, but the present inventors have solved the above problems by the following method. Settled.

That is, the present invention involves radical polymerization of a radically polymerizable silicone macromonomer and a compound having a radically polymerizable functional group and other active energy ray-reactive functional groups (hereinafter referred to as the monomer method), or , a radically polymerizable functional group and a reactive functional group (described below)
2) and a compound having a reactive functional group (1) are radically polymerized, and then the reactive functional group (1) in the reaction product is subjected to radical polymerization.
) with a compound having a reactive functional group (2) and an active energy ray-reactive functional group (hereinafter referred to as the polymer method). It is.

[Method for producing the graft polymer of the present invention] The active energy ray-curable silicone graft polymer as used in the present invention refers to a photosensitive silicone graft polymer that is cured by ultraviolet rays, etc., and a radiation-curable silicone graft polymer that is cured by radiation such as electron beams and gamma rays. Because there is a silicone-based graft polymer,
These will be explained in order below.

A method for producing a photosensitive silicone graft polymer.

A method for crudely producing a photosensitive silicone-based graft polymer is a monomer method, that is, radical copolymerization of a radically polymerizable silicone macromonomer and a monomer having a radically polymerizable functional group and a photosensitive functional group, that is, a radically polymerizable photosensitive monomer. A reactive silicone-based graft polymer is obtained by copolymerization of a radically polymerizable silicone macromonomer and a monomer having a radically polymerizable functional group and a reactive functional group, that is, a radically polymerizable active monomer. Another method involves reacting a reactive functional group (functional group derived from a radically polymerizable active monomer) in the reactive silicone graft polymer with a photosensitive group-containing compound.

The mass and monomer methods will be described.

A photosensitive silicone graft polymer can be obtained very easily by radical copolymerization of a radically polymerizable silicone macromonomer (details will be described later) and a radically polymerizable photosensitive monomer. Examples of radically polymerizable photosensitive monomers that can be used in the present invention include methacrylic acid esters of oxychalcone, and esterification reaction products of cinnamic acid and 2-hydroxyethyl methacrylate.

In these radical copolymerizations, other radically polymerizable monomers can be further copolymerized. Examples of radically polymerizable monomers that can be used include olefinic compounds such as low molecular weight unsaturated hydrocarbons such as ethylene and propylene, vinyl chlorides such as vinyl chloride and vinyl fluoride, and organic acid vinyls such as vinyl acetate. esters, styrene, styrene substitutes, and vinyl aromatic compounds such as vinylpyridine and vinylnaphthalene, acrylic acid and/or methacrylic acid (hereinafter collectively referred to as (meth)acrylic acid), esters of (meth)acrylic acid, acrolein, acrylonitrile, N - N-vinyl compounds such as vinylpyrrolidone and N-vinylcaprolactam, vinyl silicon compounds such as vinyltriethoxysilane, acrylic silicon compounds such as γ-methacryloxypropyltrimethoxysilane, etc. Also, maleic anhydride,
Examples include esters of maleic acid and fumaric acid, and macromonomers other than silicones that are cartilage-compatible.

These radically polymerizable monomers can be used alone or in combination of two or more types. 5. Conventionally known methods can be used for radical photopolymerization,
For example, a radiation irradiation method, a method using a radical polymerization initiator, etc. can be used, but a method using a radical polymerization initiator is preferable in terms of ease of polymerization operation and ease of controlling the molecular weight. Specifically, a method using a solvent is used. Polymerization method, bulk polymerization method,
The ratio of the photosensitive monomer in the graft polymer, which can be carried out by any method such as emulsion polymerization, is 1 to 1.
95% by weight is preferred, and 5 to 80% by weight is more preferred. Further, the proportion of silicone macromonomer in the graft polymer is preferably 1 to 90% by weight, and 5 to 90% by weight.
More preferably 70% by weight. If the photosensitive monomer content is less than 1% by weight, it becomes difficult to obtain excellent effects such as crosslinking properties, mechanical properties, and solvent resistance of the graft polymer. - If the amount of photosensitive motumer is more than 95% by weight, the excellent properties of silicone tend to be lost because the amount of silicone macromonomer is relatively reduced. Furthermore, if the amount of silicone macromonomer is less than 1% by weight, the excellent properties of silicone cannot be exhibited, and if it exceeds 90% by weight, polymerizability tends to deteriorate.

Next, the polymer method will be explained.
.

First, let's talk about the method for producing reactive silicone-based graft polymers. Radically polymerizable active monomers (hereinafter referred to as active monomers) having active groups such as epoxy groups, carboxyl groups, hydroxyl groups, and amine groups and radically polymerizable Silicone macromonomer (details will be explained later)
A method based on copolymerization with is preferred.

- For example, reactive silicone-based graft polymers with epoxy groups are easily obtained by copolymerization of silicone macromonomers and active monomers such as glycidyl methacrylate; reactive silicone-based graft polymers with hydroxyl groups are , by copolymerization of a silicone macromonomer with, for example, 2-hydroxyethyl methacrylate as an active monomer, and reactive silicone-based graft polymers with carboxyl groups can be readily prepared by copolymerization of a silicone macromonomer with, for example, acrylic acid as an active monomer. can get.

As described above, the reactive silicone-based graft poly is obtained by copolymerizing an active monomer and a silicone macromonomer, but the radically polymerizable monomer mentioned in the monomer method can also be used in combination.

The same method as described in the monomer method can be used as the method for the massaging radical photopolymerization.

In the obtained reactive silicone-based graft polymer, the trunk is mainly a copolymer of a radically polymerizable monomer and an active monomer, and the branches can be considered to be silicone.

The proportion of active monomers in the reactive silicone graft polymer ranges from 1 to 95% by weight, preferably from 5 to 80% by weight.
% by weight, and the proportion of silicone macromonomer in the graft polymer is from 1 to 90% by weight, preferably from 5 to 70% by weight. If the amount of the active monomer is less than 1% by weight, the amount of the photosensitive group-containing compound that reacts with the active group of the active monomer will be small, and the concentration of the photosensitive group in the resulting graft polymer will be low, resulting in poor crosslinking properties and mechanical properties. , a silicone-based graft polymer with excellent solvent resistance etc. cannot be obtained.

On the other hand, when the amount of active monomer is more than 95% by weight, the amount of silicone macromonomer is relatively reduced, so that the excellent properties of silicone are lost. Furthermore, if the amount of silicone macromonomer is less than 1% by weight, the excellent properties of silicone are lost, and if it exceeds 90% by weight, polymerizability tends to deteriorate.

Photosensitive silicone-7 is formed by the reaction of the thus obtained reactive silicone-based graft polymer with a photosensitive group-containing compound.
The photosensitive group-containing compounds used include carboxylic acid compounds with cinnamic acid residues, chalcone residues, acrylic acid residues, etc., hydroxyl compounds, isocyanate compounds, acid halides, epoxy compounds, etc. Various known methods can be employed for the reaction between the reactive silicone-based graft polymer and the photosensitive group-containing compound, including the following methods.

■ Reaction between a reactive silicone-based graft polymer having an epoxy group and a 1-rubonic acid compound containing a photosensitive group.

It is preferable to add a solvent and a catalyst to a mixture of a reactive silicone-based graft polymer and a photosensitive group-containing carboxylic acid compound and heat the mixture to carry out the reaction. As the solvent, torbone, xylene, tetrahydrofuran, methyl ethyl keto/butyl acetate, ethyl acetate, dimethylformamide, etc. can be used. The catalyst is preferably an amine compound such as triethylamine or tripropylamine, or a quaternary ammonium salt such as tetrabutylammonium bromide or triethylbenzylammonium chloride, and the amount of the catalyst is 0.01 to 100% based on the total amount of the reaction mixture and solvent. It is 5% by weight, preferably 0.005 to 6% by weight. The reaction temperature is 50 to 150°C, preferably 70 to 120°C, and the reaction time is 1 to 24 hours, preferably 2 to 10 hours.

Examples of photosensitive group-containing carboxylic acid compounds that can be used in this reaction include cinnamic acid, P-nitrocinnamic acid, furyl acrylic acid, (meth)acrylic acid, and (meth)acrylates having hydroxyl groups and dibasic acid anhydrides, such as Anhydrous Kono・
Examples include reaction products with phosphoric acid, maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.

(2) Reaction between a reactive silicone-based graft polymer having a carboxyl group and a photosensitive group-containing epoxy compound.

The reaction can be carried out smoothly by the same operation as in (D) above.

Photosensitive group-containing epoxy compounds that can be used with wood ash include glycidyl cinnamate, glycidyl (meth)acrylate, and the like.

■ Reaction between a reactive silicone-based graft polymer having a hydroxyl group and a photosensitive group-containing acid halide compound or isocyanate compound.

When using a photosensitive group-containing acid halogen compound, it may be mixed with the graft polymer and subjected to a de-hydrogenation reaction, and the photosensitive group in the photosensitive silicone-based graft polymer thus obtained is The proportion of compounds contained is
- Determined by the proportion of active monomers in the reactive silicone-based graft polymer.

In this case, it is preferable to use catalysts conveniently used in known denohydrogenation reactions, such as pyridine and triethylamine.

Photosensitive group-containing acid halogen compounds that can be used in this reaction include cinnamic chloride, P-nitrocinnamic acid chloride, furyl acrylic acid chloride, (meth)
Examples include acrylic acid chloride.

Further, when using a photosensitive group-containing isocyanate compound, it is preferable to use a catalyst used in a known urethane reaction, such as dibutyltin dilaurate or dibutyltin maleate.

Examples of the photosensitive group-containing isocyanate compound that can be used in this reaction include 2-incyanatoethyl (meth)acrylate and a reaction product of an acrylate group-containing hydroxyl compound and a diisocyanate compound.

It is preferable to use a solvent in these reactions in order to make the reaction proceed smoothly, and examples of the solvent include t, toluene,
Using xylene, tetrahydrofuran, diethyl ether, etc. Method for producing radiation-curable silicone graft polymer The photosensitive silicone graft polymer described above can be used as it is as a radiation-curable composition.

Furthermore, silicone-based graft polymers into which epoxy groups have been introduced can also be used as radiation-curable compositions. An example of a method for producing a silicone-based graft polymer having an epoxy group is the monomer method described above, ie, the method by copolymerization of a silicone macromonomer and glycidyl methacrylate. The proportion of silicone macromonomer in the graft polymer is the same as in the photosensitive silicone graft polymer, and the proportion of glycidyl methacrylate is preferably 1 to 90% by weight, and 5 to 8% by weight.
0% by weight is more preferred. In the production of this graft polymer, it is possible to further copolymerize other radically polymerizable monomers, and the radically polymerizable monomer and polymerization method are as described in I above for the photosensitive silicone graft polymer. Polymerization methods can be employed.

[Method for producing radically polymerizable silicone macromonomer]

The radically polymerizable silicone macromonomer used in the present invention has a number average molecular weight of 1.000 to 20.0 and has a polymerizable functional group at one end of the molecular chain. It refers to a relatively low molecular weight polymer mainly composed of ODD polymers, and the radically polymerizable silicone macromonomer is obtained by the following various manufacturing methods, and any of them can be used.

An example of the manufacturing method is to react a living polymer obtained by anionically polymerizing a cyclic siloxane represented by the following general formula with a radically polymerizable silicone compound represented by the following general formula @) to produce a radically polymerizable linear silicone polymer. This is a method for obtaining a monomer (hereinafter referred to as silicone macromonomer). (Patent Application No. 1120/1982).

R1 In addition, RI is a methyl group, an ethyl group or a phenyl group, and P is 3 or 4.

@) However, R2 is hydrogen or a methyl group, m is 0 or 1, R
8, R is a methyl group, ethyl group or phenyl group, n is 1
It is an integer between ~3 and 1 is an integer between 0 and 2 when m=0, and 2 when m=1.

The anionic polymerization of the cyclic siloxane may be carried out according to a conventional method, and can be easily carried out by a bulk polymerization method or a solution polymerization method using a known anionic polymerization initiator.

Examples of the cyclic siloxane represented by general 2c) include hexamethylcyclotrisiloxane, octamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclo Among them, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane are particularly preferred in terms of cost and ease of anionic polymerization. Examples of anionic polymerization initiators include organolithium compounds, alkali metal hydroxides, alkali metal alkoxides,
Known compounds such as alkali metal syralates can be used, and among these, organic lithium compounds are particularly preferred. The molecular weight of the lippin polymer obtained by anionic polymerization controls the molecular weight of the silicone macromonomer, and is controlled by the molar ratio of the cyclic siloxane and the initiator.
The molar ratio of initiator/cyclic siloxane is o, oi ~ 0.2
It is preferable. If it is less than 0.01, the silicone macromonomer will have an extremely high molecular weight (20,000 or more), and if it exceeds 0.2, the silicone macromonomer will have an extremely low molecular weight (1,0000 or more).
00 or less). The molecular weight of the silicone macromonomer is 't, oo.

If the molecular weight exceeds 20,000, the resulting silicone-based graft copolymer becomes oily and difficult to purify.

The silicone macromonomer is produced by reacting the radically polymerizable silicone compound represented by the general formula @) with the Ping polymer obtained as described above (living polymerization termination reaction).
It can be obtained by Nuclear reactions are easily carried out by mixing the two.

The radically polymerizable silicone compound represented by the general formula Q3) can be easily obtained by a known method, for example, bird CH2-c-c-ohz +43 (-0
a CH2S j(R3)3 nc-e.

(R2, form, m, R3 are the same as above) is (0) to the formula H2. C uniform CH=C
H.

; 1 0゛ (R, l −e + in are the same as above) unsaturated (
It can be obtained by a hydrosilylation reaction between meth)acrylate and H8I (ib)s HCA (R3 and n are the same as above). The amount of the radically polymerizable silicone compound used is based on general formula (B) per equivalent (1 mole) of the Rising polymerization initiator.
It is preferable that the amount of 5i-ce is 1 to 5 times the amount.

Another example of a method for producing silicone macromonomers is silicone represented by the following general formula (A') and 0.25 to 1 acrylic compound represented by the following general formula (B') per 1 mole of silicone represented by the following general formula (A').
This is a method of obtaining acrylic-modified silicone (hereinafter also referred to as silicone macromonomer) by conducting a condensation reaction with moles (Japanese Patent Application Laid-open No. 154766/1983).

(A') HO(StO)nu (R' and R2 are monovalent aliphatic hydrocarbon groups, phenyl groups, or -valent halogenated hydrocarbon groups having 1 to 10 carbon atoms. n is a positive number of 1 or more. ) (R' is a hydrogen atom or a methyl group. R4 is a methyl group,
Ethyl group or phenyl group. X is a chlorine atom, a methoxy group or an ethoxy group. ) The details of this manufacturing method are as described in the above-mentioned published patent application, and it is particularly preferable that various types of silicone represented by the general formula (A') can be easily incorporated. n in the general formula (A') is a factor that determines the molecular weight of silicone, and n is preferably 1 to 500, and 10 to 30.
If 0 exceeds 500, the resulting silicone-based graft Koa coalescence becomes oily and difficult to purify.

Examples of the acrylic compound represented by the general formula (B') include γ-methacryloxyglobylmethyldichlorosilane, γ-methacryloxypropylmethyljethoxysilane, γ-methacrylkyJ-xypropylphenyldichlorosilane, γ-methacryloxy Examples include globylethyldichlorosilane, γ-acryloxyprobylmedeldichlorosilane, and the like. These acrylic compounds are known and can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid.

Silicone represented by general formula (A') and general formula (B')
The reaction of the acrylic compound shown by proceeds smoothly by a conventional method to obtain a silicone macromonomer. That is, when X of the acrylic compound is a chlorine atom, a dehydrochlorination reaction proceeds, and when X is a methoxy group or an ethoxy group, a dealcoholization condensation reaction proceeds.

The reaction ratio of silicone and acrylic compound is 0.25 to 1 mol of acrylic compound per 1 mol of silicone IJ corn. If it is less than 0.25 mol, a large amount of unreacted silicone will remain during the production of silicone-based graft polymer, and 1
If the amount exceeds the molar amount, gelation tends to occur during the production of silicone-based graft polymers.

Furthermore, as a method for producing the silicone macromonomer preferably used in the present invention, an acrylic compound represented by the following general formula (B'') is used instead of the acrylic compound represented by the general formula (B'), and other The raw material compounds, reaction conditions, etc. are the same as the method disclosed in JP-A-58-154766 to synthesize a silicone macromonomer.

(C JP-A-59-20560) (In the above general formula, n is an integer of 1 or 3, and the other meanings of R3, R4 and X are the same as in the above general formula (B'). ) [Curing of silicone-based graft polymer by active energy rays] The silicone-based graft polymer obtained by the present invention can be easily cured by active energy rays.

The active energy ray is a general term for radiation such as electron beams, r-rays, ultraviolet rays, and the like.

The silicone-based graft polymer is cured by irradiation with active energy rays under conventional irradiation conditions. For example, by irradiating ultraviolet rays from a high-pressure mercury lamp for several seconds, it is easily cured and becomes a tough cured product that is insoluble in solvents. Further, it can be easily cured by irradiating an electron beam at an accelerating voltage of 165 KV and a dose of about 5 Mrad, and a similarly excellent cured product can be obtained.

[Examples, comparative examples and reference examples]

Example 1 Potassium metal 0.510.0128m op in flask
) and about 5 d of n-hexane were added, and 10-methanol was added dropwise over 60 minutes in a water bath under a stream of dry nitrogen. After stirring for an additional 30 minutes, excess methanol and n-hexane were distilled off under reduced pressure. Subsequently, octamethylcyclotetrasiloxane 401/ (0,135 mo form) and tetrahydrofuran 409, which had been sufficiently dehydrated with Morikilar sheep, were added, and the mixture was heated under reflux for 4 hours.

Octamethylcyclotetrasiloxane (molar ratio).

After the temperature of the reaction solution decreased to room temperature, 31 g of a 10% tetrahydrofuran solution of γ-methacryloxypropyldimethylchlorosilane (0.0141 mA of γ-methacryloxyglobildimethylchlorosilane) was gradually added dropwise, and after the dropwise addition was completed, the mixture was further heated at room temperature. Stirred for 60 minutes.

= 1.10 (equivalence ratio). After filtering out the generated potassium chloride precipitate, the filtrate was poured into methanol (1-e) to precipitate the xylicone macromonomer. After decanting and drying, 26.0 # of silicone macromonomer was obtained as a colorless and transparent oil.

The silicone macromonomer had a polystyrene equivalent number average molecular weight of 8,900 by gel permeation chromatography (hereinafter abbreviated as GPC).

Next, per 30 parts by weight of the obtained silicone macromonomer (hereinafter simply referred to as parts), 40 parts of methyl methacrylate (hereinafter referred to as MMA), 20 parts of ethyl acrylate (hereinafter referred to as EA), and glycidyl methacrylate (hereinafter referred to as GMA) as active monomers. 10 parts of 9 torrene, 260 parts of azobisisobutyronitrile (hereinafter referred to as A
1.5 parts of IBN) and 230 parts of toluene were placed in a flask equipped with a condenser and a stirrer, and polymerized in a nitrogen atmosphere at a temperature of 75°C for 10 hours to obtain 60% by weight of the epoxy group-containing reactive silicone graft polymer ( A solution (hereinafter simply referred to as -) was obtained.

Next, this epoxy group-containing reactive silicone graft polymer was reacted with acrylic acid (hereinafter referred to as AA) to obtain an acrylate group-containing silicone graft polymer. For the reaction, 66.7 parts of the epoxy group-containing reactive silicone graft polymer solution, 2 parts of AAl, and 0.33 parts of tetrabutylammonium bromide (hereinafter referred to as TBAB) were placed in a flask equipped with a condenser and a stirrer in a nitrogen atmosphere. The test was carried out by heating at a temperature of 90° C. for 5 hours. 3,450-3 by observation of infrared absorption spectrum
．． Formation of -〇H was observed at 550 cm, and 1,62
0 to 1,640cx-' based on acrylate <C=
A peak of C was observed. ``This acrylate group-containing silicone graft polymer is useful as an active energy ray-curable composition.

Example 2゜A1ω-dihydrox M3 ■ Cypolydimethylsiloxane (HO+S t O+i1H
n is flat CH.

30) 33S & (0.15 mol), γ-methacryloxypropyltrimethoxysilane 12.1 (0.05 mol), and potassium acetate 6.5 g were prepared and boiled under N2 for 1 s o
After cooling, the nuclear reactant was poured into toluene 136ON to precipitate potassium acetate, and the potassium acetate was removed by filtration.

MMA 400 parts, EA
3D 0 copies, CMA I 00 copies, AIBN 15 copies,
Add 1,530 parts of toluene to make a homogeneous solution, and under N2
Polymerization was carried out at a temperature of 5° C. for 7 hours to obtain a 30% toluene solution of an epoxy group-containing reactive silicone graft polymer.

Next, the reactive silicone graft polymer solution 667
1 part, 2 parts of AAlo, and 3.3 parts of TBAB were placed in a flask equipped with a condenser and a stirrer and reacted in N2 at a temperature of 90°C for 5 hours to obtain an active energy ray-curable acrylate group-containing silicone graft polymer. .

Example 3 As silicone, a1ω-dihydroxydimeCH8 chloropolysiloxane (HO(SiO)nH has an average n of 6)
0]0H8, 220 g (0.1 mol) of it and pyridine 9
, 49, p, (0.12 mol) in diethyl ether 4
In a solution dissolved in 0.00g, γ-methacryloxypropyldimethylchlorosilane z2. o61o, 1 mole)
A 0% diethyl ether solution was gradually added dropwise over 20 minutes at room temperature.

The reaction proceeded immediately and white crystals of pyridine hydrochloride were precipitated. After the addition was completed, the mixture was further stirred at room temperature for 1 hour, and the crystals of pyridine hydrochloride were removed by filtration.

Next, this filtrate was placed in a separatory funnel, and 500 d of water was added thereto, and the mixture was thoroughly shaken and washed with water.

After washing with water, the separatory funnel was left standing to separate the upper ether layer and the lower aqueous layer, and anhydrous sodium sulfate was added to the obtained ether layer, and the mixture was left at room temperature overnight to dehydrate. Thereafter, anhydrous sodium sulfate was removed by filtration, and the resulting filtrate was distilled under reduced pressure to remove ether, yielding colorless and transparent cisilicone monomer 205#.

Hereinafter, in exactly the same manner as in Example 1, an epoxy group-containing reactive silicone graft polymer was obtained, and then Example 1
In exactly the same manner as above, an active energy ray-curable acrylate group-containing silicone graft polymer was obtained.

Example 4 (20% silicone macromonomer obtained in Example 2)
When toluene was removed by distilling the toluene solution under reduced pressure, a colorless and transparent oily silicone macromonomer was obtained. Next, the silicone macromonomer 3 (1,M
MA6011i, 10 parts of AA, 1 part of AIBN, and 300 parts of methyl ethyl ketone (hereinafter referred to as MEK) in a stirrer,
The mixture was charged into a four-way flask equipped with a thermometer, a condenser, and an N inlet tube, and heated under N2 at a temperature of 75° C. for 8 hours to obtain a carboxyl group-containing reactive silicone-based graft polymer 251MEK solution.

Next, the reactive silicone graft polymer solution 100
14.95 parts of 0M, 5 parts of TBABo were placed in a flask equipped with a condenser, a stirrer, and a thermometer, and reacted at a temperature of 80°C for 10 hours to form an active energy ray-curable acrylate group-containing silicone graft. A polymer was obtained.

Example 5゜20 parts of the silicone macromonomer obtained in Example 1,
35 parts of MMA, 55 parts of EA, 10 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA), A I
Using 1.5 parts of B N and 230 parts of a toluene/MEK mixed solvent (1 part to 1 weight ratio) in the same manner as in Example 1, hydroxyl group-containing reactive silicone graft polymer 30
% solution was obtained. Next, 100 parts of the reactive silicone graft polymer solution, 100 parts of toluene, and 2.1 parts of pyridine.
9 parts were placed in a flask, and 20.8 parts of a 10-titoluene solution of acrylic acid chloride was gradually added dropwise at room temperature while stirring.

The reaction proceeded immediately, producing a white mass of pyridine hydrochloride. After completing the dropwise addition, the mixture was further heated at a temperature of 50°C for 5 hours.
After cooling, pyridine hydrochloride was removed by filtration to obtain an acrylate group-containing silicone graft polymer.

Example 6゜30 parts of the silicone macromonomer obtained in Example 1,
MMA 30 parts, EA 20 parts, ) (EMA 20 parts, AIB
A 50% solution of a hydroxyl group-containing reactive silicone graft polymer was obtained in the same manner as in Reference Example 4 using 5 parts of Nl, 130 parts of toluene, and 100 parts of MEK. Next, 100 parts of the reactive silicone-based graft polymer solution and 0.1 part of dibutyltin dilaurate were charged into a flask, and 72 parts of the 2-isocyanatoethyl methacrylate io*h toluene solution was added at a temperature of 80°C for 1 hour while stirring. dripped. After the dropping was completed, the nest was shaken at a temperature of 80°C for 6 hours.
A toluene solution of the acrylate group-containing silicone graft polymer was obtained. When a part of the solution was dropped onto a NaC-e plate and dried, the infrared absorption spectrum was observed, and the absorption of N0 step of 2.270 countries disappeared and became -1 at 5,550α-1.
An absorption peak of NH- is observed, from t600 to "L 620
(An absorption peak based on C=C of methacrylate was observed at 14R-'.

Example 1 The procedure was exactly the same as in Example 2, except that 667 parts of the epoxy group-containing reactive silicone graft polymer 50 titoluene solution obtained in Example 2, 20.9 parts of cinnamic acid, and 4.0 parts of TBAB were used. An active energy ray-curable silicone-based graft polymer containing cinnamic acid residues was obtained.

Example 8゜20% liter of silicone macromonomer obtained in Example 2
・per 1000 parts of toluene solution, 200 parts of MMA, EA
200 parts of GMA, 400 parts of GMA, 2 parts of AlBN, and 1530 parts of a mixed solvent of toluene/MEK=171 (weight ratio) were added to make a homogeneous solution, and polymerized under N at a temperature of 75°C for 7 hours to form an epoxy group-containing silicone. A graft polymer solution was obtained.

Cough graft polymers are useful as active energy radiation curable compositions.

Example 9 30 parts of the silicone macromonomer obtained in Example 6,
A flask was charged with 20 parts of MMA, 20 parts of EA, 2 parts of AlBN, and 233 parts of toluene, and polymerization was carried out in exactly the same manner as in Example 8 to obtain an active energy ray-curable silicone graft polymer.

Comparative Example 1 7100 parts of α,ω-dihydroxypolydimethylsiloxa H3, 50 parts of styrene, 67 parts of butyl acrylate
1 part, 33 parts of GMA, and 0.75 parts of di-t-butyl peroxide were placed in a flask equipped with a condenser and a stirrer, and the reaction was started at a temperature of 122°C under N2, but 2 hours after the start of the reaction, the viscosity decreased. It rose significantly and became gel-like. After cooling, an attempt was made to dissolve the reaction product in toluene, but the mixture remained cloudy due to the presence of a considerable amount of undissolved matter.

As described above, it has been extremely difficult to produce reactive silicone-based graft polymers by the hydrogen abstraction method.

Reference Example 1 The acrylate group-containing silicone-based graft polymer obtained in Example 1 was coated on a glass plate using a toluene solution using an overcoater.

After air drying at room temperature for one day, a transparent coating film with a thickness of 10 μm was obtained. An electron beam was applied to the coating film at an accelerating voltage of 165 KV and 5 Mrad.
It was irradiated and cured at a dose of . This coating did not dissolve in l.luene. The coating film was crosslinked and strong.

The electron beam irradiation device is Energy 5sciencesI.
Made by nC, EIJCTROCURTAIN-CB 150
was used.

Reference Example 2 3 parts of benzoin ethyl ether was added to 100 parts of the toluene solution of the acrylate group-containing silicone graft polymer obtained in Example 2, and the mixture was coated on a glass plate using a bar coater.

After air-drying at room temperature for one day (film thickness 10μ), the coating was applied with a power of 80W/cm.
A high-pressure mercury lamp with an output of 1 (made by Nippon Battery ■)
Cure Lamp, HI2ON ozone type condensing type lamp] was irradiated with ultraviolet rays for 6 seconds in the air at a distance of 8 cm to cure. This coating film was insoluble in toluene and was strong.

(3) Effects of the invention According to the present invention, active energy ray-curable silicone graft polymers can be industrially advantageously obtained by relatively simple means, and the obtained silicone graft polymers can be cured by active energy rays. [It forms a cured product with extremely excellent physical properties.

The silicone-based graft polymer is used in films, rubber, sealants, paint vehicles, etc., and has water repellency,
Demonstrates water resistance, heat resistance, weather resistance, mold release properties, slip properties, etc., as well as mechanical strength, hardness, solvent resistance, abrasion resistance,
Demonstrates excellent performance such as

In addition, in the field of surface-modifying additives for various plastic films and paints, the above-mentioned silicone-based graft polymers have excellent ability to migrate and concentrate on the surface of substrates, and on the other hand, they have excellent affinity with substrate polymers. Therefore, the silicone-based graft polymer that has migrated and concentrated on the surface of the base material does not easily bleed from the surface.

Claims (1)

[Claims] 1. Radical polymerization of a radically polymerizable silicone macromonomer and a compound having a radically polymerizable functional group and other active energy ray-reactive functional groups, or the above-mentioned macromonomer, a radically polymerizable functional group, and the reaction described below. A compound having a reactive functional group (2) and a reactive functional group (1) is radically polymerized, and then the reactive functional group (1) in the reaction product is combined with the reactive functional group (2) and a reactive functional group (1). A method for producing an active energy ray-curable silicone graft polymer, which comprises reacting with a compound having an active energy ray-reactive functional group.