JP2853423B2 - Method for producing reactive microgel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a high-resolution, high-sensitivity resist material useful for the production of printing plates, printing plates such as flexographic plates, semiconductor devices and the like, or binders for paints and inks. Also useful as a reactive filler and excellent in water resistance, a polymerizable unsaturated double bond,
The present invention relates to a method for producing a reactive myrogel having a reactive group such as a hydroxyl group or a carboxyl group.

[0002]

2. Description of the Related Art Microgels have a size such as a colloid, for example, a diameter of 0.001 to 10 μm, generally 1 μm.
The following gelled or crosslinked polymer particles have attracted attention in recent years as new polymer materials synthesized by emulsion polymerization. Microgels having no reactive groups on the surface serve only as a filler, and were used only for the purpose of improving the strength of the material. However, in 1975, the functional groups were added to the surface by Funke of Germany. Since the synthesis of existing microgels, microgels have received a great deal of attention and have been studied by macromolecular scientists around the world. (W. Obrecht, U. Seitz, W. Fu
nke, Am.Chem.Soc., Div.Polym.Chem., Prepr. 16 (1),
149 (1975)).

The microgel synthesized by Funke is obtained by polymerizing a monomer having two or more polymerizable unsaturated double bonds under very mild conditions by emulsion polymerization and remaining on the surface without reacting with the polymerizable unsaturated double bond. The bond was modified with another reagent and converted into various reactive functional groups. As an example, a method has been proposed in which borane is used to convert to a hydroxyl group, hydrogen halide is used to convert to a halogen group, and ozone is used to convert to a carboxyl group. However, since these reactions do not occur in a system in which water is present, the microgel is separated from the aqueous dispersion, purified, dried, and then dispersed in an organic solvent such as DMF and pyridine to react with various reagents. It must be converted into a reactive group, which is too laborious and very expensive, so that its use as an industrial material is limited.

Also, Yamazaki et al. Have attempted to synthesize a reactive microgel in one step by emulsion polymerization of a polyfunctional monomer having a hydroxyl group, an epoxy group, etc. and a polymerizable unsaturated double bond. (Yamazaki, Hattori, surface 1987, 25,
86). However, the types of functional groups that can be introduced by this method are very limited. Particularly, functional groups having polymerizable unsaturated double bonds are attacked by radicals during emulsion polymerization and react. It was difficult to synthesize a reactive microgel having

Accordingly, the present inventors have conducted intensive studies and have found an addition reaction that occurs in water. By utilizing the addition reaction, the microgel can be isolated from an aqueous dispersion without separating other functional groups other than epoxy groups. For example, the present inventors have found a production method capable of easily and quantitatively providing a functional group such as a polymerizable unsaturated double bond, a hydroxyl group, and a carboxyl group to the microgel surface. However, the polymer emulsifier used in the above method is generally inferior in emulsifying power as compared with the low-molecular surfactant, so that depending on the material used for the core, it is difficult to microgel even if the polymer emulsifier is increased. there were.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a low-molecular surfactant and a high-molecular emulsifier together, the core material was difficult to synthesize conventionally. The present inventors have found that a reactive microgel can be synthesized even with this method, and have reached the present invention.

[0007]

That is, the present invention provides a method for synthesizing a monomer having a polymerizable unsaturated double bond by emulsion polymerization using a quaternary ammonium salt-containing polymer emulsifier and a low-molecular surfactant. Microgel fine particles (A)
And a compound (B) having an epoxy group which reacts with a quaternary ammonium salt in one molecule and at least one other reactive functional group in one molecule. .

In the present invention, the monofunctional monomer having a polymerizable unsaturated double bond used in synthesizing the microgel fine particles (A) includes (a)
(Meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate.
Aruriru butyl, (meth) Aruriru acid hexyl, (meth) acrylate, octyl (meth) C ₁ -C ₁₈ alkyl esters of (meth) acrylic acid and lauryl acrylate: glycidyl (meth) acrylate: allyl (meth)
Alkenyl esters of C ₂ -C ₈ (meth) acrylic acid acrylate: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate of (meth) C ₂ -C ₈ hydroxyalkyl esters of acrylic acid: allyloxy (meth) C ₃ -C ₁₉ hydroxy alkenyl esters :( meth) acrylic acid acrylic acid such as ethyl (meth) acrylate, (b) styrene as a vinyl aromatic compound, alpha-methyl styrene, vinyl toluene, p- Chlorostyrene, etc. (c) Other acrylonitrile, methacrylonitrile, methyl isopropenyl ketone: vinyl acetate, vinyl propionate, vinyl pivalate and the like.

Next, polyfunctional monomers and oligomers having two or more polymerizable unsaturated double bonds for three-dimensionally cross-linking the inside of the microgel fine particles (A) include (a)
(Meth) acrylates include tri (methyl) acrylate of trimethylolpropane, di (meth) acrylate of glycols, poly (meth) acrylate of polyols, and di (meth) acrylic acid of polyurethanes (C) at least two or more polymerizable unsaturated double bonds such as butadiene, isoprene, chloroprene, divinylbenzene and diallyl phthalate; Oligomers with
Is mentioned. These monomers are appropriately selected according to the desired physical properties, and may be used alone, respectively, or
Species or more can be used in combination.
The use ratio of the monofunctional monomer to the polyfunctional monomer is usually 100: 0.1 to 50, preferably 1 in molar ratio.
00: 0.1 to 10.

The quaternary ammonium salt-containing polymer emulsifier used in synthesizing the microgel fine particles (A) is 3
A compound having a quaternary amino group is neutralized with an acid and quaternized. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, propionic acid, butyric acid, and (meth) acrylic acid.

Examples of the quaternary ammonium salt-containing polymer emulsifier include reactive monomers having an amino group such as 2,2-dimethylaminoethyl (meth) acrylate and 2,2-diethylaminoethyl (meth) acrylate, and other reactive monomers. Water-soluble monomer such as methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, etc. C ₁ -C ₁₈ alkyl esters of acrylic acid: C ₂ -C ₈ (meth) acrylic acid such as allyl (meth) acrylate
Alkenyl ester: C ₂ -C ₈ hydroxyalkyl ester of (meth) acrylic acid such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate: C ₃ of (meth) acrylic acid such as allyloxylethyl (meth) acrylate -C ₁₉ alkenyloxyl alkyl ester: obtained by copolymerizing one or more vinyl monomers selected from (meth) acrylic acid and the like, followed by neutralization with an acid, natural polymers such as chitosan, and polyethylene Examples thereof include those obtained by neutralizing a polymer containing an amino group such as a synthetic polymer such as imine with an acid.

These polymer emulsifiers may be used as such or by reacting a part of a quaternary ammonium salt with a compound containing an epoxy group and a polymerizable unsaturated double bond such as glycidyl (meth) acrylate. A double bond can be introduced and used as a reactive emulsifier. By using a reactive emulsifier, the emulsifier itself can be fixed to the core when the inside of the microgel fine particles (A) is three-dimensionally crosslinked. By fixing an emulsifier (shell) inside (core) of microgel fine particles (A), a film using reactive microgel, resist material containing reactive microgel, strength of reactive filler, water resistance And various resistances such as abrasion resistance can be improved. These polymer emulsifiers are used in an amount of 0.1 to
50% by weight, preferably 3 to 20% is used.

The low molecular surfactant used in combination with the quaternary ammonium salt-containing polymer emulsifier includes a nonionic surfactant and a cationic surfactant. Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene cetyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene such as polyoxyethylene nonyl phenyl ether. Examples include ethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester such as sorbitan monolaurate, sorbitan stearate, and sorbitan trioleate, glycerin fatty acid ester, and polyoxyethylene fatty acid ester.

Examples of the cationic surfactant include hydrochlorides of primary amines such as monomethylamine, monoethylamine and monostearylamine, hydrochlorides of secondary amines such as dimethylamine, diethylamine and distearylamine, trimethylamine, triethylamine, and the like. Hydrochlorides of tertiary amines such as stearyl dimethylamine, hydrochlorides of ethanolamines such as monoethanolamine, diethanolamine and triethanolamine, hydrochlorides of polyethylene polyamines such as ethylenediamine and diethylenetriamine, amines such as pyridine, morpholine and hydrazine And the like.

The low-molecular surfactant is preferably used in an amount of 0.1 to 50%, more preferably 0.1 to 20%, based on the monomer. The temperature of the emulsion polymerization is 50 to 95 ° C, preferably 65 to 80 ° C. In the emulsion polymerization, the solid content of the monomer and the emulsifier is 10 to 50%, preferably 15 to 3%.
0%. In the present invention, the particle size of the microgel formed by emulsion polymerization is usually 1 as measured by a light scattering method.
0 to 500 nm.

The quaternary ammonium salt present on the surface of the microgel particles (A) thus formed and the compound (B) having an epoxy group and at least one other reactive functional group in one molecule To introduce a reactive functional group on the surface of the microgel fine particles. Compound (B)
Epoxy compounds having a polymerizable unsaturated double bond such as glycidyl (meth) acrylate, N-glycidyl (meth) acrylamide, glycidyl allyl ether, 1,2-epoxy-5-hexene, and epoxy having a hydroxyl group such as glycidol. Compounds and epoxy compounds having a carboxyl group such as epoxy succinic acid.
These compounds (B) are appropriately selected according to the desired physical properties, and may be used alone or in combination of two or more. 1 to 10 with respect to the quaternary ammonium base on the microgel particle surface
The reaction can be performed at a free ratio up to 0 mol%. This reaction is completed only by mixing the epoxy compound with the microgel emulsion and stirring the mixture at a temperature of 30 to 90 ° C, preferably 60 to 80 ° C for 2 hours or more. Thus, the present invention has an advantage that various reactive functional groups can be easily imparted to the surface of the microgel even in an aqueous dispersion.

The reactive microgel according to the present invention is provided as an aqueous dispersion or as an organic solvent dispersion in which water is partially or entirely removed by azeotropic distillation with benzenes, alcohols, ketones, and the like. When it is desired to use the microgel in a dry state, the microgel can be obtained by an ordinary method, preferably by a method of coagulating the microgel, washing and drying the coagulated material to obtain a fine powder, or a spray drying method. For the purpose of satisfying the required characteristics of various uses, a monomer, an oligomer, and a polymer compound having a polymerizable unsaturated double bond in the reactive microgel obtained in the present invention,
Alternatively, a polymer compound having no polymerizable unsaturated double bond or the like may be added and used as long as the original characteristics are not impaired.

[0018]

EXAMPLES The present invention will be described in more detail with reference to Examples. In the examples, “part” and “%” indicate “part by weight” and “% by weight”, respectively.

Example 1 (1) Preparation of cationic polymer emulsifier In a nitrogen atmosphere, 100 parts of 2-ethylhexyl methacrylate, 50 parts of 2-dimethylaminoethyl methacrylate and 200 parts of 2-propanol were stirred in a 2 liter reaction vessel. At 80 ° C. 1.6 parts of azobisisobutyronitrile (hereinafter referred to as AIBN) was added and the mixture was maintained for 2 hours, then 0.4 parts of AIBN was added, and then the reaction mixture was maintained at 80 ° C. for 4 hours to complete the polymerization. After cooling to room temperature, a mixture of 38.2 parts of acetic acid and 1000 parts of deionized water was added, heated and azeotropically distilled to remove 2-propanol and water to a solid content of 20%.

(2) Preparation of Reactive Cationic Polymer Emulsifier 18.1 Parts of glycidyl methacrylate are added to the cationic polymer emulsifier synthesized in (1), and the mixture is heated to 70 ° C. in an air atmosphere and maintained for 2 hours. Thus, a methacryl group-pending cationic polymer emulsifier was obtained.

(3) Synthesis of non-reactive microgel 50 parts of R-45ACR-LC (dimethacrylate modified polybutadiene manufactured by Idemitsu Petrochemicals Co., Ltd.) and 50 parts of Emulgen 420 (polyoxyethylene olein ether manufactured by Kao Corporation) 2.5 parts, 19.2 parts of the aqueous solution of the reactive cationic polymer emulsifier synthesized in (2), 14 deionized water
8.2 parts were heated to 80 ° C. in a nitrogen atmosphere with stirring in a 500 ml reaction vessel. 0.5 parts of a 3% aqueous solution of azobisamidinopropane dihydrochloride (hereinafter referred to as AAPD) was added thereto, and the mixture was maintained for 2 hours. Then, 0.5 part of a 3% AAPD aqueous solution was added. After completion of the addition, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization. The measurement result of the particle size by the light scattering method was about 50 nm.

(4) Synthesis of Reactive Microgel After the non-reactive microgel aqueous dispersion synthesized in (3) was left overnight, 1.1 parts of glycidyl methacrylate was added and heated to 70 ° C. in an air atmosphere. By holding for 2 hours, a reactive microgel sample (1) was obtained.

Example 2 (1) Preparation of cationic polymer emulsifier 100 parts of 2-ethylhexyl acrylate, 50 parts of 2-dimethylaminoethyl acrylate and 200 parts of 2-propanol were stirred in a 2 liter reaction vessel in a nitrogen atmosphere. At 80 ° C. 1.6 parts of azobisisobutyronitrile (hereinafter referred to as AIBN) was added and the mixture was maintained for 2 hours, then 0.4 parts of AIBN was added, and then the reaction mixture was maintained at 80 ° C. for 4 hours to complete the polymerization. After cooling to room temperature, a mixture of 38.2 parts of acetic acid and 1000 parts of deionized water was added, heated and azeotropically distilled to remove 2-propanol and water to a solid content of 20%.

(2) Preparation of reactive cationic polymer emulsifier To the cationic polymer emulsifier synthesized in (1), 18.1 parts of glycidyl methacrylate is then added, and the mixture is heated to 70 ° C. in an air atmosphere and maintained for 2 hours. Thus, a methacryl group-pending cationic polymer emulsifier was obtained.

(3) Synthesis of non-reactive microgel 50 parts of R-45ACR-LC (dimethacrylate modified polybutadiene manufactured by Idemitsu Petrochemical Co., Ltd.) and Emulgen 810 (polyoxyethylene octylphenyl ether manufactured by Kao Corporation) Was heated to 80 ° C. in a nitrogen atmosphere with stirring in a 500 ml reaction vessel with 19.2 parts of the aqueous reactive cationic polymer emulsifier synthesized in (2) and 148.2 parts of deionized water. . A 3% aqueous solution of azobisamidinopropane dihydrochloride (hereinafter referred to as AAPD) was added to a 0.1% aqueous solution.
5 parts were added and kept for 2 hours. Then, 0.5 part of a 3% AAPD aqueous solution was added. After the addition is completed, the reaction mixture is brought to 80 ° C for 4 hours.
The polymerization was completed by holding for a time. The measurement result of the particle size by the light scattering method was about 50 nm.

(4) Synthesis of Reactive Microgel After the non-reactive microgel aqueous dispersion synthesized in (3) was left overnight, 1.1 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C. in an air atmosphere. By holding for 2 hours, a reactive microgel sample (2) was obtained.

Example 3 In place of emulgen 420 of Example 1, Rheodor TW
A reactive microgel sample (3) was obtained in the same manner as in Example 1 except that -S106 (polyoxyethylene sorbitan monostearate manufactured by Kao Corporation) was used.

Example 4 A reactive microgel sample (4) was obtained in the same manner as in Example 1 except that distearylamine acetate was used instead of emulgen 420 in Example 1.

Comparative Example 1 In the synthesis of the non-reactive microgel of Example 1 (3), no emulgen 420 was used, and instead, the aqueous solution of the reactive cationic polymer emulsifier synthesized in Example 2 was used.
(Solid content of about 20%) was synthesized in various amounts shown below under the other conditions in the same manner as in Example 1. However, in any case, the gel was formed into a yogurt state to form a microgel. I couldn't do that. Therefore, it was not possible to proceed to the step (4) of Example 1. The amount of the aqueous solution of the reactive cationic polymer emulsifier synthesized in (2) of Example 1 was
19.2, 50, 100, 160 or 200 parts.

Comparative Example 2 In the synthesis of the non-reactive microgel of Example 2 (3), no emulgen 810 was used, and instead, the aqueous solution of the reactive cationic polymer emulsifier synthesized in Example 2 (2)
(Solid content of about 20%) was synthesized in various amounts shown below under the other conditions in the same manner as in Example 1. However, in any case, the gel was formed into a yogurt state to form a microgel. I couldn't do that. Therefore, it was not possible to proceed to the step (4) of Example 2. The amount of the aqueous solution of the reactive cationic polymer emulsifier synthesized in (2) of Example 2 was
19.2, 50, 100, 160 or 200 parts.

[Evaluation of Reactive Microgel] The reactive microgel samples (1), (2),
(3), (4) Five parts of Darocure 2959 (trade name, manufactured by Merck) were added to 100 parts of each solid content to prepare a microgel-dispersed film having a thickness of about 300 μm by a casting method. It was cured by irradiating with ultraviolet rays of cm ² . The films thus obtained are referred to as film samples 1, 2, 3, and 4, respectively. The film samples 1, 2, 3, and 4 were immersed in ion-exchanged water, isopropyl alcohol (abbreviated as IPA), and an aqueous solution of sodium carbonate (pH 9) at 20 ° C. for 24 hours, and the weight increase rate was measured. Table 1 shows the results. The hardness was measured according to JIS-K6301. The weight increase rate is ((weight after immersion for 24 hours / weight before immersion) −
1) It was determined by × 100.

[0032]

[Table 1]

[0033]

According to the present invention, a material which was conventionally difficult to form a microgel can be formed into a reactive microgel, and the total emulsifier amount can be reduced. As a result, the range of choice of the core material has been expanded, and it has become possible to meet various demands for photosensitive materials such as paints, inks, photocurable adhesives, printed boards, and printing plates.

Claims (5)

(57) [Claims] The method according to claim 1 polymerizable unsaturated monomer having a double bond, the microgel particles (A) was synthesized by emulsion polymerization using a quaternary ammonium salt-containing polymer emulsifier and a low molecular surfactant, 1 method for producing a reactive microgel which comprises reacting a compound having an epoxy group and at least one other reactive functional groups that react with a quaternary ammonium salt in a molecule (B). 2. A method for producing a reactive microgel of claim 1, characterized in that it comprises a quaternary ammonium salt-containing compound is a polymerizable unsaturated double bond. 3. A 1 at least one other reactive functional group polymerizable unsaturated epoxy groups which react with a quaternary ammonium salt in a molecule and at least one compound having other reactive functional group (B) 3. The method for producing a reactive microgel according to claim 1, wherein the reactive microgel is a double bond. Wherein at least one other reactive functional group 1 epoxy group reactive with a quaternary ammonium salt in a molecule and at least one compound having other reactive functional group (B) is a hydroxyl group Claim 1 characterized by the following:
Or the method for producing a reactive microgel according to 2. 5. The method for producing a reactive microgel according to claim 1, wherein the low molecular surfactant is a nonionic surfactant or a cationic surfactant.