JPS59217714A - Hardenable composition and hardening method - Google Patents

Abstract

PURPOSE:To provide the titled composition composed of a hydrophobic graft polymer obtained by using a macromonomer as a component, a hydrophilic graft polymer, and a radically polymerizable component, and capable of modifying the surface of a polymeric material to hydrophobic or hydrophilic by curing. CONSTITUTION:The objective composition is composed of (A) a hydrophobic graft polymer and/or hydrophilic graft polymer obtained by using a macromonomer (e.g. the compound of formula) as a component and (B) a radically polymerizable component such as a methacrylic acid ester. The surface of the cured product can be made hydrophobic or hydrophilic by polymerizing and curing the composition in a hydrophobic or hydrophilic atmosphere corresponding to the hydrophobic or hydrophilic nature of the graft polymer in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable composition and a method for curing the composition.

When a polymeric material is used as a cured product, surface treatment suitable for the intended use is often required, and techniques for making the surface of the polymeric material hydrophobic or hydrophilic are required.

Conventional 1. Surface modification methods for polymeric materials include immersing the polymeric material in an oxidizing liquid such as a mixture of chromic acid and sulfuric acid to introduce hydrophilic groups onto the surface, or adding hydrophilic groups to the surface of the polymeric material in an appropriate etching solution. Chemical methods such as immersing the material and preferentially dissolving only the specific components that make up the polymer and creating many dents on the surface of the polymer, corona discharge treatment on the surface of the polymer, radiation, light, etc. A method of grafting the surface of a polymer material using plasma irradiation, a physical method such as a mechanical roughening method, a method of coating the surface of a polymer material with a coupling agent such as an oligomer, a polymer, or a silane, a method of coating the surface of a polymer material with a surfactant or silicone, etc. ,
Methods such as incorporating fluorine compounds (oil, resin, etc.) have been used. Among these methods, chemical methods cannot treat all polymeric materials, and require ingenuity to modify only specific polymeric materials or to modify only specific surfaces of polymeric materials.

Physical methods require special equipment, so
In the coating method, the modification of the surface of the polymer material is temporary, the modification effect is not durable, the coated substance is easily removed, and a thin coating film may be created. There are many problems such as difficulty in Even with the rolling method, the durability of the modification effect on the surface of the polymer material is by no means satisfactory, and in order to maintain a sufficient modification effect on the surface of the polymer material, a large amount of addition is required. The original performance of the material may be impaired. Furthermore, these conventional methods for surface modification of cured products such as polymeric materials require a special process for surface modification, leading to an increase in cost.

Furthermore, these conventional cured product surface modification techniques (hereinafter referred to as conventional techniques) can be applied to, for example, polyester-type oligopolyacrylate (consisting of polyhydric alcohol, polycarboxylic acid, and acrylic acid) with ultraviolet rays or electron beams. When applied to cured coatings and molded products, when applied to methyl methacrylate cast resin plates, when unsaturated polyester is mixed with styrene, etc. (usually, such mixtures are unsaturated). When applied to coatings and molded products obtained from saturated polyester resins (called saturated polyester resins), or to coatings and molded products obtained from diallyl phthalate prepolymers, the following methods are recommended: There is a problem.

When conventional techniques are applied to these coatings, they are either not applicable to extremely thin coatings or may damage the substrate of the coating. Furthermore, these molded products are often cast-cured and have many problems, such as when they have complex shapes and it is very difficult to apply conventional techniques when it is desired to modify only a specific surface.

The present invention was developed as a result of intensive research in view of these drawbacks of the prior art.

That is, the present invention consists of the following two inventions.

1. A curable composition comprising a hydrophobic graft polymer and/or a hydrophilic graft polymer and a radically polymerizable component, in which the graft topo IJ-r- is produced using a macromonomer as one component (hereinafter simply referred to as a graft polymer). A curable composition characterized in that it is

2. A curable composition comprising a hydrophobic graft polymer and/or a hydrophilic graft polymer and a Udocal polymerizable component, wherein the graft polymer is produced using a macromonomer as one component. ,
A curing method characterized by making the surface of a cured product hydrophobic or hydrophilic by polymerizing and curing in a hydrophobic or hydrophilic environment corresponding to the hydrophobicity or hydrophilicity of the graft polymer in the composition. .

The present invention uses a polymer obtained from a hydrophobic component or a hydrophilic component and a radically polymerizable component as a polymer additive that can easily modify the surface of a cured product and has an excellent modification effect and sustainability of the modification effect. This work was made based on the fact that a graft polymer having a structure consisting of an anchor component that is compatible with the macromonomer is useful, and that it is particularly advantageous if the graft polymer can be manufactured using a macromonomer as one component. It is.

In a composition in which a graft polymer is added to a radically polymerizable component (i.e., the curable composition of the present invention), depending on the type of graft polymer and the environment in which the curable composition comes into contact, the graft polymer may be attached to the surface of the curable composition. Transfer and concentrate. On the surface of a curable composition in which a hydrophobic graft polymer is added to a radically polymerizable component, the hydrophobic graft polymer is concentrated on the surface in a hydrophobic environment, and the hydrophobic graft polymer is not concentrated on the surface in a hydrophilic environment.

Similarly, on the surface of a composition in which a hydrophilic graft polymer is added to a radically polymerizable component, the hydrophilic graft polymer is concentrated on the surface in a hydrophilic environment, and the hydrophilic graft polymer is not concentrated on the surface in a hydrophobic environment.

Furthermore, in a curable composition in which a hydrophobic graft polymer and a hydrophilic graft polymer are simultaneously added to the radically polymerizable component, the hydrophobic graft polymer is present on the surface in a hydrophobic environment, and the hydrophilic graft polymer is present in a hydrophilic environment on the surface. is concentrated.

By polymerizing and curing a curable composition in which the surface of the graft polymer is concentrated using a radical polymerization method suitable for the intended use, a cured product whose surface has been modified to be hydrophobic or hydrophilic can be obtained very easily.

In the present invention, the surface of the cured product is made hydrophobic or hydrophilic by polymerizing and curing the curable composition in a hydrophobic or hydrophilic environment corresponding to the hydrophobicity or hydrophilicity of the graft polymer in the composition. When using a hydrophobic graft polymer, it is done in a hydrophobic environment, when a hydrophilic graft polymer is used, it is done in a hydrophilic environment, and when a hydrophobic graft polymer and a hydrophilic graft polymer are used together. By polymerizing and curing in a hydrophobic or hydrophilic environment, the surface of the cured product can be modified to be hydrophobic or hydrophilic.

In order to more effectively modify the surface of the cured product according to the present invention in a short time, it is preferable to quickly transfer and concentrate the graft polymer onto the surface of the radically polymerizable component. The type and amount of the radically polymerizable monomer, the viscosity, the environment in which the curable composition comes into contact with it, the temperature and time, etc. can be mentioned, but since graft polymers have excellent migration ability, the above By appropriately controlling various factors, a larger amount of the graft polymer can be quickly transferred and concentrated on the surface of the radically polymerizable component.

For example, in a curable composition in which a hydrophobic graft polymer is added to a highly viscous radically polymerizable component, by slightly heating the composition in a hydrophobic environment, the hydrophobic graft polymer can be added to the surface in contact with the hydrophobic environment. It can be quickly concentrated.

On the other hand, in the case of a low-viscosity radically polymerizable component, it can be concentrated at room temperature in a very short time.

In an embodiment of the present invention, for example, polyester is heated in air for a short time and then polymerized and cured by ultraviolet rays or electron beams in a nitrogen atmosphere.The surface in contact with the air atmosphere is made hydrophobic and has excellent water repellency. shows.

In addition, methyl methacrylate casting resin is obtained by pouring a curable composition in which a graft polymer is added to a low polymer of methyl methacrylate (syrup commonly used for casting) into a mold and polymerizing and curing it in a conventional manner. The surface of the plate can be controlled by the type of graft polymer used and the type of mold with which it is in contact during polymerization and curing. In this case, one side of the plate advancement mold is made of a hydrophobic material (e.g. Teflon),
If the other side is made of a hydrophilic material (e.g. glass) and a hydrophobic graft polymer is used, one surface of the resulting methyl methacrylate cast resin plate becomes hydrophobic and exhibits excellent water repellency, while the other surface is made of polyester. A method of modifying the surface of a cured product to make it hydrophilic using a curable composition containing a hydrophilic graft polymer is to apply the curable composition to the surface of the cured product and cover it with a polar plastic film such as nylon. There is a method of peeling off the film after polymerization and curing.

As the hydrophobic component of the hydrophobic graft polymer that can be used in the present invention, hydrocarbons, perfluorocarbons, and silicones are effective. Monomers that become these hydrophobic components include, for example, methacrylic acid or long-chain alkyl acrylate, Fatty acid vinyl, CnF, n+1 (C)-
I2) l! 0COCH=CH2 (mixture of n = 4-14), CF3 (CF,)7 (CM, ), 0COCH
=CH2, (cps)tcp(crt)+. (CH,)
30COCH=CI (2, radically polymerizable linear silicone oligomer disclosed in Japanese Patent Application No. 57-188227 and Japanese Patent Application No. 58-1120, Japanese Patent Application No. 57-3585)
acrylic modified silicone, P-tertiary-'tilstyrene, dibasic acids, glycols, diamines, etc., which have a long-chain alkyl component, perfluoroalkyl component, or silicone component, as disclosed in No. 7 and Japanese Patent Application No. 129075/1982. Examples include polycondensation or polyaddition monomers.

In addition, monomers serving as the hydrophilic component of the hydrophilic graft polymer that can be used in the present invention include monomers having carboxyl groups, hydroxyl groups, amino groups, acid amide groups, sulfonic acid groups, phosphoric acid groups, polyoxyethylene groups, etc. Examples include acrylic acid, methacrylic acid, hydroxyethyl methacrylate, acrylamide, dimethylaminoethyl acrylate, vinylpyridine, N-methylpyro, hydrone, vinylsulfonic acid, diethylvinyl phosphate, polyoxyethylene. Examples include vinyl monomers such as monomethacrylate, and polycondensation and polyaddition monomers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The method for synthesizing the hydrophobic and hydrophilic graft polymers used in the present invention is a macromonomer method.

Compared to conventionally known graft polymer synthesis methods such as the chain transfer method, radiation grafting method, and polymer initiator method, the graft polymer synthesis method using the macromonomer method has a lower content of homopolymers in the branch and trunk components. few.

■The molecular weight of the core, the overall molecular weight of the graft polymer, and the weight ratio of branches to trunk can be well controlled.

■You can freely select the combination of branch components and trunk components according to your purpose.

This is because it has the following features.

In the present invention, the macromonomer refers to an oligomer with a relatively low molecular weight (1000 to 10,000 in number average molecular weight) that has a polymerizable functional group at one end of the molecular chain, and the graft polymer refers to the macromonomer. - is manufactured using at least one component.

Examples of the terminal polymerizable functional group of the macromonomer in the present invention include vinyl polymerization types such as acryloyloxy, methacryloyloxy, allyloxy, and styryl, and polycondensation addition types such as dicarboxy and dihydroxy.

Further, the monomer constituting the macromonomer can be selected depending on the purpose, and examples thereof include alkyl acrylate, alkyl methacrylate, styrene, oxyethylene, dimethylsiloxane, and the like.

Graft polymers are composed of hydrophobic or hydrophilic components (hereinafter referred to as functional components) and anchor components that are compatible with the cured product. It is obtained by copolymerizing a functional monomer (hereinafter abbreviated as a functional monomer) and a 7-monomer (hereinafter abbreviated as an anchor monomer) as an anchor component. It may be a macromonomer.

3 Regarding the synthesis of the hydrophobic graft polymer preferably used in the present invention, taking as an example a method for synthesizing a hydrophobic graft polymer containing fluorine in the molecular chain by the macromonomer method, for example, methyl methacrylate is synthesized in the coexistence of thioglycolic acid. Radical polymerization to give a molecular weight of 1.000 to 10.0
A one-terminated carboxylic acid prepolymer of No. 00 is obtained, and this is reacted with glycidyl methacrylate to produce a macromonomer having a methacrylic acid ester type terminal group.

For this macromonomer, fluoroacrylate (CFs(-CF, )n-C)I was added as a copolymerization component.

C'H4C0CH=C) (,, mixture of n=4 to 12)
By using this method, a graft polymer can be obtained in which the trunk is a hydrophobic component and the branches are polymethyl methacrylate.

In this case, the fluoroacrylate is the functional monomer and the macromonomer is the anchor monomer.

In addition, as a method for synthesizing a hydrophobic graft polymer containing silicone in its molecular chain, copolymerization of a one-terminated methacryloyloxy-1 bale linear silicone oligomer and methyl methacrylate obtained according to Japanese Patent Application No. 57-188227 is mentioned. I can do it. In this case, the one-end methacryloyloxy-linear silicone oligomer is the functional monomer and macromonomer, and methyl methacrylate is the anchor monomer.

The content of hydrophobic monomer residues in these hydrophobic graft polymers is preferably 95 to 90% by weight, more preferably 20 to 70% by weight.

The fluorine content in the hydrophobic graft polymer for calculating the content of hydrophobic monomer residues is the amount of fluorine-containing mo/mer determined by the NMIR spectrum of the fluorine-based graft polymer (for example, regarding the amount of fluoroalkyl acrylate, refer to (See Example 2), the silicone content is an analytical value obtained by firing a silicone-based graft polymer and assuming that the silicone is Sin.

A hydrophobic graft polymer comprising less than 5% by weight of hydrophobic monomer residues is used in the curable composition, and then
The effect of modifying the surface of the resulting cured product cannot be sufficiently exerted, and when a hydrophobic graft polymer with a hydrophobic monomer residue content of more than 90% by weight is used, the solubility in radically polymerizable components becomes poor. Furthermore, the resulting hydrophobic graft polymer is expensive. This is because most of the cost of raw materials for the hydrophobic graft polymer used in the present invention is accounted for by the price of raw materials containing fluorine, silicone, etc.

On the other hand, the method for synthesizing the hydrophilic graft polymer preferably used in the present invention is a macromonomer method, for example, using acrylic acid as a copolymerization component with a macromonomer having a methacrylic acid ester type terminal group obtained by the above method. In this way, a graft polymer is obtained in which the trunk is a hydrophilic component and the branches are polymethyl methacrylate. In this case, acrylic acid is the functional monomer and the macromonomer is the anchor monomer.

The amount of hydrophilic component in the hydrophilic graft polymer is
The content of hydrophilic monomer residues in the hydrophilic graft polymer is preferably 3 to 80% by weight, and more preferably 5 to 50% by weight. When a hydrophilic graft polymer with a hydrophilic monomer residue content of less than 3% by weight is used, it can be expected to have a hydrophilic effect on the surface of the resulting cured product and, when applied to the cured product, to have an adhesive effect with the cured product. Furthermore, if a hydrophilic graft polymer with a hydrophilic monomer residue content of more than 80% by weight is used, the solubility in the radically polymerizable component will be poor.

The radically polymerizable component in the present invention is a radically polymerizable monomer alone or a mixture thereof with an oligomer or a polymer, and is mainly composed of a radically polymerizable monomer, and specifically includes the following: Examples include [A] to [D].

[A] Polymerizable acrylic ester and/or methacrylic ester monomer (hereinafter collectively referred to as (meth)acrylic ester monomer) Radically polymerizable (meth)
It is an acrylic acid ester monomer, and the following (1) to (11)
) can be exemplified.

(11) Mono(meth)acrylate 7-to-cI (2=c-c-o-ma1 (where Ro is hydrogen or methyl group, and horse has 1 to B carbon atoms)
an alkyl group, \1 (2) Compound having the structure of the general formula M-G-OH The meanings of the symbols M and G are as follows.

M: Acrylic acid or methacrylic acid residue G: Glycol residue (3) Polyester poly(meth)acrylate.

The details are in JP-A-49-120889,
r(1) polyester polyacrylate and/or polyester polymethacrylate".

(4) Poly(meth)acrylate, which is an ester of polyhydric alcohol and acrylic acid or methacrylic acid.

The details are given in Japanese Patent Application Laid-Open No. 120889/1989.
[■] Polyhydric alcohol polyacrylate and/or polyhydric alcohol polymethacrylate".

(5) Epoxy poly(meth)acrylate.

The details are as described in JP-A-50-9686 as "(2) Epoxy polyacrylate and/or epoxy polymethacrylate".

(6) Reaction products of acrylic acid or methacrylic acid with monoepoxides and acid anhydrides.

The details are given in Japanese Patent Application Laid-Open No. 50-9686 [(
3) Reaction products of acrylic acid or methacrylic acid 9 and monoepoxides and acid anhydrides.”
As explained.

(7) Has a carboxyl group in the molecule and has a boiling point of 2 at normal pressure.
Mono(meth)acrylate at 50°C or higher.

The details of this substance are explained in JP-A-5[]-9968 as "(5) monoacrylate and/or monomethacrylate having a carboxyl group in the molecule and having a boiling point of 250°C or higher at normal pressure". As it is.

(8) Mono(meth)acrylate having a terminal epoxy group.

The details of this are as described in JP-A-50-9686 as "(6) Monoacrylate and/or monomethacrylate having terminal epoxy group".

(9) Polyurethane poly(meth)acrylate.

The details of this compound are as described in Japanese Patent Publication No. 45-124000, and the compound represented by the following general formula is applicable.

1 Here, the meanings of the symbols in the above formula are as follows.

R1: hydrogen or methyl group R': divalent organic group selected from the group consisting of C, -t lower alkylene, phenylene and naphthylene groups.

X; selected from groups having -O- and -N- groups; R selected from hydrogen and C1~ lower alkyl groups;

B; Substituted or unsubstituted alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkaryl and double.

A polyvalent organic group selected from a group with a ring group.

to-21 n; integer from 2 to O Ring polyamide (meth)acrylate.

This includes the compound represented by the following general formula described in Japanese Patent Publication No. 48-37246, glycidyl (
They are obtained by condensing meth)acrylates with linear polymers of aliphatic polycarboxylic acids, which also contain saturated alicyclic groups, and saturated aliphatic diamines or amino alcohols.

However, the meanings of the symbols in the above formula are as follows.

n: an integer of 1 to 14 A: a divalent group selected from the group consisting of -0- and -NH-, but one polyamide molecule must have at least one of the above -NH- groups shows.

R: Indicates the bond amount between two adjacent carboxyl groups selected from the group consisting of a single bond and a divalent aliphatic saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. .

R1: represents a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms.

R11; hydrogen atom or methyl group.

X: represents a hydrogen atom and an acyl group of R''lCO.

R"' represents a hydrogen atom or an aliphatic hydrocarbon having 1 to 18 carbon atoms.

(11) Poly(meth)acrylate of addition alcohol of phenol compound and oxide compound.

This is based on the general formula described in JP-A-49-122550 (wherein the aromatic group is a benzene ring or other aromatic group with or without a substituent, respectively, and R1 and H are hydrogen). , alkyl, aryl or a halogen atom, horse represents hydrogen or a methyl group, and R6 is hydrogen, an alkyl or alkoxy group or a halogen atom,
n is an integer of 1 to 20).

The (meth)acrylates (1) to (11) described in "Soil" can be used alone or in combination of two or more as the main component of the monomer, but the composition of the present invention further includes industrial In order to increase the value, for example, the following polymerizable compounds can be blended depending on the purpose. Examples of diacetone acrylamide, acrylamide, and nitrogen-containing (meth)acrylate include dimethylaminoethyl (meth)acrylate and dimethylamine propyl (meth)acrylate.

(BE Methyl methacrylate-based casting resin board production 2≠ Monomer mixture of methyl methacrylate and methyl methacrylate prepolymer (usually called syrup).

(C) Unsaturated polyester resin Unsaturated polyester with styrene, methyl methacrylate,
Dissolved in vinyltoluene, α-methylstyrene, t-butylstyrene, etc.

(D) Examples of the diallyl phthalate monomer include diallyl phthalate, diallyl phthalate prepolymers, and mixtures thereof.

The amount of graft polymer added to the radically polymerizable component is
It is preferably 0.01 to 10% by weight based on the component, and 0.0% by weight.
More preferably 5 to 5% by weight.

If the amount of the graft polymer added is less than 0.01% by weight, the effect of modifying water repellency, oil repellency, hydrophilicity, etc. on the surface of the cured product will not be sufficiently exhibited, and if it exceeds 10% by weight, the original performance of the cured product will not be exhibited. This is not desirable because it has a negative effect on the product and increases the cost.

In addition, when using a hydrophobic graft polymer and a hydrophilic graft polymer together, from the viewpoint of improving water repellency, oil repellency, hydrophilicity, etc. on the surface of the cured product, it is necessary to 50 to 500 parts by weight of the graft polymer is preferred.

The method of mixing the graft polymer and the radically polymerizable monomer is not particularly limited, but it is preferable to add the graft polymer to the radically polymerizable component. There are methods such as dissolving the polymer in a small amount of a suitable solvent and adding it to the radically polymerizable monomer.
Either method may be used.

Regarding the environment during polymerization and curing, hydrophobic environments include the surface of fluoropolymer; for example, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, ethylene-tetra Surfaces of films and sheets of fluoroethylene copolymers, te)rafluoroethylene-berfluorovinyl ether copolymers, surfaces coated with fluorine compounds on metals, glass, etc., and gases such as air and nitrogen. I can give it to you.

In addition, hydrophilic environments include glass, metals, ceramics,
Surfaces such as polar plastics (such as nylon) can be mentioned.

In addition, the cured product in the present invention includes a cured product obtained by polymerizing and curing the curable composition, and other cured products such as the above-mentioned fluoropolymers, glasses, metals, ceramics, polar plastics, and the like.

As a method for polymerizing and curing the curable composition, conventionally known methods can be used, including a heating method using a radical polymerization initiator,
Any method may be used, such as a method of redox polymerization curing using a radical polymerization initiator and a polymerization curing accelerator in combination at around room temperature, a method using ultraviolet rays or electron beam irradiation, or a method using a combination of these methods.

The radical polymerization initiator is preferably an organic radical polymerization initiator, such as peroxyketal, hydroperoxide, dialkyl peroxide, 7diasilver oxide, peroxydicarbonate,
Examples include azo compounds represented by peroxy esters and azobisisobutyronitrile.

In the method using ultraviolet irradiation, a known sensitizer is used as a radical polymerization initiator, and in the case of electron beam irradiation, there is no need to use a radical polymerization initiator.

The amount of radical polymerization initiator used is based on the curable composition.
It is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight.

As the accelerator used in redox polymerization curing in combination with the radical polymerization initiator, known ones can be used, such as organic amines, organic acids, amides, imides, thioamides, thioureas, Examples include metal salts.

The curable composition of the present invention can impart excellent water repellency, oil repellency, and hydrophilicity to the surface of the cured product without impairing the original performance of the cured product, and due to the presence of the anchor component, it migrates and concentrates on the surface of the cured product. The resulting graft polymer does not easily separate from the surface of the cured product, and can maintain the effect of modifying the surface of the cured product, and can also improve adhesion to the cured product.

Moreover, according to the curing method of the present invention, the above-mentioned excellent surface modification effect can be obtained using a much simpler method than in the prior art.

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples.

In addition, all the percentages written on each side represent % by weight, and the parts represent parts by weight.

Reference Example 1 Synthesis of terminal methacrylate type methyl methacrylate macromonomer A glass flask K equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a gas inlet, 10 parts of methyl methacrylate (hereinafter abbreviated as MMA), and acetone (1
75%)-toluene mixed solvent were charged, and after introducing N, 0.5 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator and 0.32 parts of thioglycolic acid as a chain transfer agent were added under reflux. 9 minutes to start one go. During the subsequent 4.5 hours, 90 parts of MMA was continuously added dropwise, and 2.88 parts of thioglycolic acid was dissolved in 7 parts of toluene and added in 9 portions every 30 minutes. Polymerization was carried out by adding 5 parts in 3 portions every 1.5 hours. Thereafter, the mixture was refluxed for 2 hours to complete the polymerization, and a polymer solution having the following structural formula [1] was obtained. The reaction temperature was 77-87°C. A part of the reaction solution was reprecipitated with n-hexane, dried, and the acid value was measured, and it was found to be 0.
It was 340 kg equivalent/g.

C0O-CI(a) Next, after distilling off a part of the acetone from the above reaction solution, 0.5% of triethylamine as a catalyst and 200 ppm of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the acid value was 1%. .2 times the mole of glycidyl methacrylate was added and reacted under reflux (approximately 110°C) for 11 hours.The reaction rate determined from the decrease in acid value was 96%.The reaction solution was diluted with 100 times the amount of n- The macromonomer 90 having the following structural formula [11] was prepared by adding it to xane, precipitating it, and drying it under reduced pressure at 80°C.
I got the department. The molecular weight in terms of polystyrene determined by gel permeation chromatography (hereinafter referred to as GPC) is 2.
, 840 (number average) and 6.470 (weight average). The hydroxyl value was 0.350 .mu.-equivalent/ly.

Blasphemy?驇CT(,0CO-C=C)(2 Reference Example 2 Synthesis of fluorine-based graft polymer by macromonomer method (Part 1) Reference for synthesis of fluoroalkyl acrylate (trunk)/methyl methacrylate (branch)-<C-type graft polymer Apparatus K similar to Example 1, 70 parts of Mac 10 monomer obtained in Reference Example 1, 30 parts of fluoroalkyl acrylate of the following structural formula Clit), 270 parts of trifluorotoluene (C,H,CF,), AIB No. , and reacted under reflux (approximately 100° C.) for 5 hours while introducing N2.

[1) CF3(=CF2)-CM, -CH2-0CO-
CH=CH.

A mixture of n = 4 to 12, (average value of n 7), this reaction solution was poured into 10 times the volume of methanol to precipitate it, and 80
The mixture was dried under reduced pressure at °C to obtain 67 parts of a graft polymer.

This product showed a single peak by GPC, and the polystyrene equivalent molecular weight was 10,800 (number average) and 21.
700 (weight average).

In addition, trifluorotoluene was added as an internal standard substance, and the H-NMR spectrum was measured in CDC/3 solvent.
The content of the MMA unit in the graft polymer was determined from the peak area ratio of 10-CH3 to H in the unit.
It was 60%. The remaining 240% was made up of fluoroalkyl acrylate.

In this way, a fluorine-based graft polymer with a fluorine content of 40% was obtained. In addition, a fluorine-based graft polymer having a fluorine content of 31% and a molecular weight of about 10,000 (number average) was also synthesized by the same procedure by changing the amount of fluoroalkyl acrylate charged.

Reference Example 3 Synthesis of hydrophilic graft polymer Synthesis of acrylic acid+MMA (trunk)/MMA (branch)-comb-shaped graft polymer.

In a device similar to Reference Example 1, 40 parts of the macromonomer obtained in Reference Example 1, 15 parts of acrylic acid, 45 parts of MMA, and 2 parts of an ethanol (25 vol 1%)-tetrahydrofuran mixed solvent were added.
70 parts of AIB No. and 78 parts of AIB No. were charged, N was introduced, and the mixture was reacted under reflux (52 to 66°C) for 6 hours.

This reaction solution was poured into 10 times the volume of n-hexane, precipitated, and dried under reduced pressure at 80°C to obtain 55 parts of a graft polymer.

This product showed a single peak by GPC, and the molecular weight in terms of 3 polystyrene was 8,700 (number average) and 24,800 (weight average).゛Also, the acid value is 1
It was 1211P equivalent/g.

Reference Example 4 Synthesis of silicone-based graft polymer α,ω-dihydroxydimethylpolysiloxane?・Silicone C with [n of HO(SiO)nH is 30 on average]
H.

22ON (0,1 mol) and viridi 79.49 #(0,
A 10% diethyl ether solution of 12.06 # (0.05 mol) of γ-methacryloxypropylmethyldichlorosilane was gradually added dropwise over 20 minutes at room temperature to a solution of 12.06 # (0.05 mol) of γ-methacryloxypropylmethyldichlorosilane dissolved in 400 sl of diethyl ether.

The reaction proceeded immediately and white crystals of pyridine hydrochloride 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, put this filtrate into a separatory funnel, add 500 d of water, shake well, and wash with water. 3 After washing with water, leave the separatory funnel still and separate the upper ether layer and the lower aqueous layer. Then, add anhydrous sodium sulfate to the resulting ether layer,
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 225 g of transparent and colorless acrylic modified silicon.

Next, the obtained acrylic modified silicone and MMA were copolymerized. For copolymerization, 50 parts of the acrylic modified silicone, MM
Add 50 parts of A, 1.0 part of azobisisobutyronitrile, and 600 parts of toluene to condensate? -1 The mixture was placed in a flask equipped with a stirrer and reacted for 24 hours at a temperature of 80°C in a nitrogen atmosphere. After the reaction, toluene and unreacted MMA were removed by vacuum distillation to obtain a solid reaction product. Next, from the reactant, n-
Unreacted acrylic modified silicone was extracted with hexane and dried under reduced pressure to obtain 81 parts of a white powdery silicone graft polymer.

This silicone-based graft polymer was soluble in toluene, xylene, and thinner.

Further, as a result of analysis, the amount of silicone contained in this silicone-based Graftpo S Lif was 40% as dimethylpolysiloxane, and the number average molecular weight in terms of polystyrene was 90,000.

For silicone analysis, approximately 0.29 g of silicone-based graft polymer was accurately weighed in a platinum crucible, approximately 311 It of concentrated sulfuric acid was added, the mixture was placed in an electric furnace and heated at 700° C. for 2 hours, and the silicone was determined as Sin.

Moreover, the molecular weight is a value determined by liquid chromatography.

Example 1 and Comparative Example 1 The fluorine-based graft polymer with a fluorine content of 61% obtained in Reference Example 2 was treated with the following radically polymerizable monomer (1).
, (II), the weight composition ratio of (1) is (I)/(11)/
One part was added to 100 parts of the mixture of (III)=42/2B/30, and the mixture was stirred at 50°C for 20 minutes to dissolve.

This composition was coated on a glass plate using a bar coater, and after being left in the air at room temperature for 30 minutes, an electron beam irradiation device (E
Manufactured by energy 5sciences Inc, ELECT
It was cured by irradiation using a ROCURTAIN, CB 150) at an accelerating voltage of 165 KV and a line of 5 Mr. ad. The thickness of the resulting coating film was 20μ.

Example 1
It was shown as In addition, the same radically polymerizable monomer mixture without the fluorine-based graft polymer was treated in the same manner, and the surface (air surface) of the resulting coating film (control product) and the surface of the coating film that was in contact with the glass plate trap. The contact angle with respect to water is shown in Table 1 as Comparative Example 1.

Table-1 The radically polymerizable monomers used are as follows.

(1) Polyfunctional polyester acrylate manufactured by Toa 7 Synthetic Kagaku Kogyo ■ Trade name Aronix-8060 (1) CI-T3 (J-I, C (CH20CO (J
(=CT(,).

Further, the contact angle was measured at 25° C. using a contact angle measuring device including a goniometer. Hereinafter, all contact angle measurements on each side were performed using this method.

As can be seen from Table 1, the coating film surface obtained by the method of the present invention has excellent water repellency, and the surface of the coating film that was in contact with the glass plate is not significantly different from that of the control product. .

Example 2 The same fluorine-based graft polymer as in Example 1 was used in Example 1.
1 for 100 parts of the same radically polymerizable monomer mixture as
1 part was added and stirred at 50°C for 20 minutes to dissolve. This composition was coated on a glass plate using a bar coater. Next, this was heated in air at 70° C. for 5 minutes, and then immediately irradiated with an electron beam in the same manner as in Example 1. The thickness of the resulting coating film is 20μ
Met.

B The contact angle of this coating surface with water is 115°, n
- The contact angle for decane was 55°.

It can be seen that the coating film surface has excellent water and oil repellency.

Example 6 The same fluorine-based graft polymer as in Example 1 was used in Example 1.
1 for 100 parts of the same radically polymerizable monomer mixture as
1 part was added and stirred at 50°C for 20 minutes to dissolve. This composition was coated on a Teflon sheet, and the same operations as in Example 1 were carried out to obtain a coating film with a thickness of 20 μm. The contact angle on the surface of this coating (air surface) was 100°, and the contact angle on the surface of the coating that was in contact with the Teflon sheet (measured by peeling the coating from the Teflon sheet) was 115°. .

It can be seen that in environments where the paint base is extremely hydrophobic, such as a Teflon sheet, the surface of the paint film in contact with the base can also be made hydrophobic.

Example 4 and Comparative Example 2 A methyl methacrylate monomer solution containing 20% polymethyl methacrylate (Mitsubishi Rayon ■9 trade name BR-60) dissolved in methyl methacrylate was used as a radically polymerizable monomer. A composition was prepared by dissolving 1 part of the fluorine-based graft polymer having a fluorine content of 40% obtained in Reference Example 2 in 100 parts of the monomer solution. Next, 0.5 parts of benzylthiourea was added and dissolved in 10 parts of the composition, and then 2 parts of cumene hydroperoxide were added and mixed to obtain a polymerizable composition. Next, the polymerizable composition was
The mixture was then poured into a mold for casting and curing consisting of a Teflon sheet, a polyethylene terephthalate film, and a rubber backing, and polymerized and cured at room temperature for one day. A polymethyl methacrylate resin plate with a thickness of 21 was taken out from the mold, and the contact angle on the surface of the polymethyl methacrylate resin plate is shown in Table 2. Example 4
It was shown as In addition, the same monomer solution without the addition of the fluorine-based graft polymer was operated in the same manner, and the contact angle of the obtained resin plate (control product) surface is shown in Table 2. Comparative Example 2
It was shown as

IIl, O Table 2 As shown in Table 2, one surface of the polymethyl methacrylate resin plate obtained by the method of the present invention has excellent water repellency, and the other surface has excellent water repellency. 4 on the surface of one side of the resin plate.
It can be seen that it has been modified.

Example 5 and Comparative Example 6 Same methyl methacrylate monomer solution 10 as in Example 4
To 0 parts, 5 parts of the hydrophilic graft polymer obtained in Reference Example 6 and 0.5 parts of benzylthiourea were added and dissolved, and further 2 parts of cumene hydroperoxide were added and mixed to obtain a polymerizable composition.

4/ Next, the polymerizable composition was immediately poured into a cast-curing mold made of glass, polyethylene terephthalate film, and rubber backing, and heated at room temperature for 12 hours and then at 90° C. for 1 hour to polymerize and cure.

Next, the formwork was immersed in warm water at 50°C for 1 hour, and the polymethyl methacrylate resin board was taken out from the formwork and air-dried at room temperature for 2 days. The contact angle on the surface of the polymethyl methacrylate resin plate thus obtained is shown in Table 6 as Example 5. or,
The same monomer solution without the addition of the hydrophilic graft polymer was operated in the same manner, and the contact angle on the surface of the resulting resin plate (control product) is shown in Table 3 as Comparative Example 3.

Table 3 2 As seen from Table 3, the surface of the polymethyl methacrylate resin plate obtained by the method of the present invention was found to be more hydrophilic than the surface of the control product, especially in contact with the glass of the formwork. It can be seen that the surface of the polymethyl methacrylate resin plate on the other side was strongly hydrophilized.

Example 6 Methyl methacrylate monomer solution 10 same as Example 4
1 part of the silicone-based graft polymer obtained in Reference Example 4 and 0.5 part of benzylthiourea were added and dissolved in 0 parts of the mixture, and 2 parts of cumene hydroperoxide were further added and mixed to obtain a polymerizable composition.

Thereafter, the same operation as in Example 4 was performed to obtain a polymethyl methacrylate resin plate. The contact angle of the surface of the polymethyl methacrylate resin plate that was in contact with Teflon was 110°,
The contact angle of the surface in contact with polyethylene terephthalate was 71°.

It was found that only one surface of the polymethyl methacrylate resin plate was provided with water repellency.

3 Example 7 and Comparative Example 4 A monomer solution (manufactured by Mitsui Toatsu Chemicals, trade name Nyster R-235) in which unsaturated polyester, polymerization curing accelerator, etc. were dissolved in styrene was used as a radically polymerizable monomer. A composition was prepared by dissolving 0.5 part of the fluorine-based graft polymer having a fluorine content of 61% obtained in Reference Example 2 in 100 parts of the monomer solution.

Next, 1 part of methyl ethyl ketone peroxide (manufactured by NOF ■, trade name: Vermec H) was added and mixed to 100 parts of the composition to obtain a polymerizable composition.

Next, the polymerizable composition was immediately poured into a mold for casting and curing consisting of a Teflon sheet, a polyethylene terephthalate film, and a rubber backing, and polymerized and cured for one day at room temperature.

A cured unsaturated polyester resin plate with a thickness of 2III was taken out from the mold, and the contact angle of the resin plate surface was shown in Table 4. Example 7
It was shown as

In addition, the same seven-mer solution without the addition of the fluorine-based graft polymer was operated in the same manner, and the contact angle on the surface of the resulting resin plate (control product) is shown in Table 4 as Comparative Example 4.

Table 4 Example 8 and Comparative Example 5 Diaryl phthalate 50 as a radically polymerizable monomer
Diaryl phthalate prepolymer (manufactured by Osaka Soda ■,
Using a monomer solution in which 50 parts of Daiso Tsubu L (trade name) was dissolved, 0.0.
A composition was prepared in which 5 parts were dissolved. Next, 1 part of benzoyl peroxide was added and dissolved in 100 parts of the composition to obtain a polymerizable composition.

Next, the polymerizable composition was poured into a mold for casting and curing consisting of a Teflon sheet, Borie 5 ethylene terephthalate film, and rubber backing, and 9 parts were polymerized and cured at 0° C. for 4 hours. After cooling, a hardened diallyl phthalate resin plate with a thickness of 2 mm was taken out from the formwork, and the contact angle on the surface of the resin plate was measured.
5 as Example 8.

Further, the same monomer solution without the addition of the fluorine-based graft polymer was operated in the same manner, and the contact angle on the surface of the resulting resin plate (control product) is shown in Table 5 as Comparative Example 5.

Table 5 Example 9 To 100 parts of the same methyl methacrylate monomer tb solution as in Example 4, the fluorine content obtained in Reference Example 2 was added to 40 parts.
% fluorine-based graft polymer, 5 parts of the hydrophilic graft polymer obtained in Reference Example 3, benzylthiourea 0.5 parts
Add and dissolve 1 part of cumene hydroperoxide, and then add 2 parts of cumene hydroperoxide.
parts were added and mixed to obtain a polymerizable composition.

Next, the polymerizable composition is immediately poured into a mold for casting and curing consisting of a Teflon sheet, a glass plate, and a rubber backing.
The mixture was heated at room temperature for 12 hours and then at 90° C. for 1 hour to effect polymerization and hardening. Next, the formwork was immersed in warm water at 50°C for 30 minutes, and the polymethyl methacrylate resin plate was taken out from the formwork and air-dried at room temperature for 2 days. The contact angle on the surface of the polymethyl methacrylate resin plate thus obtained is shown in Table 6 as Example 9.

Table-6 Patent Applicant Toagosei Chemical Industry Co., Ltd. J-7 Procedural Amendment ゛July 22, 1980 Director General of the Patent Office Kazuo Wakasugi 1, Indication of Case 1989 Patent Application No. 91574 2, Invention Name of curable composition and curing method 3, ? Relationship with the case of a person who makes corrections Patent applicant address: 1-14-1-4 Nishi-Shinbashi, Minato-ku, Tokyo, Detailed explanation of the invention in the specification subject to amendment, column 5, Contents of amendment (1) Description "Ro" on page 21, line 3 and line 8 of the same page
Correct it to rRJ.

(2) Replace “Ro” on page 22, line 12 of the statement box with “
Correct it as “R””.

(3) Change rk+rJ on page 30, line 9 of the statement box to “
■” and correct it.

Claims (1)

[Scope of Claims] t A curable composition comprising a hydrophobic graft polymer and/or a hydrophilic graft polymer and a radically polymerizable component, wherein the graftpo9-r- is produced using a macromonomer as one component. A curable composition characterized by: 2. A curable composition comprising a hydrophobic graft polymer and/or a hydrophilic graft polymer and a radically polymerizable component, wherein the graft polymer is produced using a macromonomer as one component. A curing method characterized by making the surface of a cured product hydrophobic or hydrophilic by polymerizing and curing in a hydrophobic or hydrophilic environment corresponding to the hydrophobicity or hydrophilicity of the graft polymer in the composition.