JP2804582B2 - Active energy ray polymerizable unsaturated resin composition and curable composition containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an active energy ray-polymerizable unsaturated resin composition and an active energy ray-curable composition.

(Prior art and its problems) Conventionally, a composition containing an inorganic filler has been used as a photocurable composition. The inorganic filler is blended in a large amount in order to obtain a photocured film having excellent physical properties such as hardness and heat resistance. However, the light transmittance of the composition is reduced by the inorganic filler, so that the curability of the coating is deteriorated, or the coating is brittle and porous, and the mechanical properties, water resistance, adhesion, and chemical resistance of the coating are reduced. However, there is a disadvantage that the method is inferior.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a compound having colloidal silica, an alicyclic epoxy group and an active energy ray-polymerizable unsaturated group. Is reacted in the presence of a metal chelate and / or metal alkoxide, whereby the silanol group in the colloidal silica component can easily react with the alicyclic epoxy group, and the curability obtained by using this The composition was excellent in curing by irradiation with active energy rays, and the mechanical properties of the formed film, water resistance, chemical resistance, and adhesion were found to be excellent, and the present invention was completed. .

That is, the present invention relates to colloidal silica (A) dispersed in an organic solvent, one alicyclic epoxy group and one
A compound (B) having one or more active energy ray-polymerizable unsaturated groups in a molecule and a metal chelate and / or metal alkoxide (hereinafter referred to as “metal compound (C)”)
Abbreviated. ), An active energy ray-polymerizable unsaturated resin composition (hereinafter abbreviated as “resin (I)”). Furthermore, a powdery active energy ray-polymerizable unsaturated resin composition (hereinafter abbreviated as “resin (II)”) obtained by removing the solvent and an active ingredient containing these resin compositions as essential components The present invention relates to an energy ray-curable composition.

Colloidal silica (A) used in the resin (I) of the present invention
As the toner, those having an average particle diameter of about 0.005 μm to 0.1 μm obtained by dispersing silica powder having a silanol group on the particle surface in an organic solvent can be used. If the average particle size is larger than about 0.1 μm, the cured product may become cloudy or the sedimentation stability may be reduced, while if the average particle size is smaller than about 0.005 μm, the viscosity of the composition increases. It is not preferable because handling becomes difficult. The organic solvent can be used without any particular limitation as long as it can disperse silica stably. Preferred specific examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, and n-heptyl alcohol. _C1-6 monohydric alcohols such as, for example; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc .; ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether Ethers such as dimethyl ether and diethylene glycol dimethyl ether; amides such as N, N-dimethylformamide; and dicarboxylic acids such as acetonitrile. Such as Lil acids and the like. Organic solvents other than those described above, for example, aromatic hydrocarbons, esters, ketones, and the like can also be used in combination.

The compound (B) used in the resin (I) of the present invention is a compound having one alicyclic epoxy group and one or more active energy ray-polymerizable unsaturated groups in one molecule. As the active energy ray polymerizable unsaturated group, any group can be selected without particular limitation as long as it is a group which is activated by an active energy ray such as visible light, ultraviolet ray, electron beam or the like to cause a polymerization reaction. Specifically, a vinyl group, an allyl group, a (meth) acryloyl group,
(Meth) acrylamide group and the like.

Representative examples of the compound (B) include the following.

[In each formula, R ¹ represents a hydrogen atom or a methyl group. R ²
Represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. m is 1
Indicates an integer of 10. In the above, ² having 1 to 6 carbon atoms represented by R 2
As the monovalent aliphatic saturated hydrocarbon group, a linear or branched alkylene group such as methylene, ethylene, propylene,
Examples thereof include a tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, And the like.

When a compound having two or more alicyclic epoxy groups in one molecule is used as the compound (B), the compound is reacted with colloidal silica (A) in the presence of the metal compound (C). This is not preferable because the system thickens and gels. Also, in place of the alicyclic epoxy group When a polymerizable unsaturated group-containing compound having an aliphatic epoxy group such as is used, the reactivity between the epoxy group and the silanol group in the colloidal silica component is poor, so that the colloidal silica component and the unsaturated group-containing compound component Is not sufficiently bonded, and a cured film having excellent appearance and performance cannot be obtained.

The colloidal silica (A) and the compound (B) can be appropriately compounded according to the required film performance. Usually, the total solid content of both is 80 to 20% by weight, preferably 80 to 30% by weight. The compounding ratio of the compound (B) is 20 to 80% by weight, preferably 20 to 70% by weight. When the colloidal silica (A) is less than 20% by weight and the compound (B) is more than 80% by weight, the breaking performance such as hardness and heat resistance is not sufficient, while the colloidal silica (A) is more than 80% by weight, If the amount of the compound (B) is less than 20% by weight, cracks may occur in the coating and transparency may be poor, which is not preferable.

The metal compound (C) used in the resin (I) of the present invention is at least one compound selected from metal chelates and metal alkoxides.

As the metal chelate, preferably, at least one of an aluminum chelate compound, a titanium chelate compound and a zirconium chelate compound can be used. As the metal chelate compound, for example, those described in JP-A-1-129060 can be used. Specifically, diisopropoxyethyl acetoacetate aluminum, tris (ethylacetoacetate) aluminum, isopropoxybis (ethylacetoacetate) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum, tris (n-propylacetate) Aluminum acetate, tris (isopropylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, monoethylacetoacetate bis (acetylacetonato) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum , Acetylacetonato bis (propionylacetonato) aluminum, diisopropoxy
Bis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetonato) titanium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetonato) zirconium,
Preference is given to tetrakis (ethylacetoacetate) zirconium.

As the metal alkoxide, aluminum, titanium, zirconium, sodium, potassium, calcium, a metal such as lithium, an alkoxy group preferably used compounds are C _{1 to 18} alkoxy group attached.
These compounds may be associated. Specifically, aluminum triisopropoxide, aluminum tri-se
c-butoxide, aluminum tri-n-butoxide,
Titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide,
Titanium tetra-tert-butoxide, zirconium tetraisopropoxide, zirconium tetra-n-propoxide, zirconium tetraisobutoxide, zirconium tetra-n-butoxide, zirconium tetra-
tert-butoxide and the like are preferred.

The metal compound (C) is used in an amount of 0.01 to 1 based on 100 parts by weight of the total solid content of the colloidal silica (A) and the compound (B).
0 parts by weight, preferably 0.1 to 5 parts by weight.

The resin (I) of the present invention is, for example, a colloidal silica (A)
And the compound (B) is heated at a reaction temperature of about 40 to 130 ° C. for about 1 to 10 hours in the presence of the metal compound (C).

The colloidal silica (A) component in the resin composition thus obtained may or may not contain a silanol group.

The resin (II) of the present invention can be used as a powdery resin composition by removing the solvent containing the organic solvent.

The curable composition of the present invention contains the resin (I) and / or the resin (II) as an essential component, and can be used alone or in the form of another curable composition such as the curable composition described below. Can be used in combination with. These may be in any form such as a solution or a powder of water or an organic solvent.

Next, a curable composition using the resins (I) and (II) in combination with another resin will be described.

In the curable composition of the organic solution using the resin (I), those having no silanol group in the resin (I) include other active energy ray-polymerizable unsaturated group-containing resins other than those described above. A compound having at least one active energy ray polymerizable unsaturated group-containing monomer, or a compound having a silanol group in the resin (I) having a functional group reactive with the silanol group Alternatively, a mixture of the above-mentioned other active energy ray-polymerizable unsaturated group-containing resin and / or monomer can be used.

As the other resin, a conventionally known resin can be appropriately selected and used. Specifically, oligomers such as epoxy acrylic oligomers, polyester oligomers, urethane acrylic oligomers, acrylic oligomers, oligoester acrylic oligomers, ether acrylic oligomers, butadiene oligomers, and acrylic oligomers containing a splan ring are preferably used. it can. It has an average of one or more active energy ray-polymerizable unsaturated groups in one molecule, and has a molecular weight of 100 to 20,000.

As the monomer, a conventionally known monomer can be appropriately selected and used. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate,
2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, (meth) acrylamide, monofunctional vinyl monomers such as styrene, ethylene glycol, trimethylolpropane,
Examples thereof include di- or triesters of polyhydric alcohols such as glycerin and pentaerythritol with (meth) acrylic acid.

The functional group-containing compound has at least one or more functional groups selected from, for example, an epoxy group, a silanol group, a hydrolyzable group directly bonded to silicon, a hydroxyl group, an isocyanate group, and the like, which react with a silanol group, in one molecule. It has one or more. When the compound is used, a curing reaction by irradiation with active energy rays and a curing reaction by heating occur at the same time, so that there is an effect that coating film performance and the like are improved.

As the functional group-containing compound, conventionally known compounds can be appropriately selected and used. Specifically, as a compound having an epoxy group, A homopolymer of the compound (B) or a copolymer with another monomer [for example, the monofunctional monomer except (meth) acrylic acid]; Thisonox 201;
Same as left 206 (above, Chisso products, alicyclic epoxy resin)
Such alicyclic epoxy compounds can be suitably used. In addition to the above, an aliphatic epoxy group-containing compound having no alicyclic epoxy group can be used, but the alicyclic epoxy group-containing compound is less reactive than the alicyclic epoxy group-containing compound. It is desirable to use them in combination. The compound having a silanol group or a hydrolyzable group directly bonded to silicon (for example, an alkoxy group, an aryloxy group, an acyloxy group, etc.) is preferably a silanol group and / or
Or having an alkoxysilane group, specifically, a polysiloxane-based macromonomer described in JP-A-62-197423, an alkoxysilane-containing vinyl monomer described in JP-A-63-108049. A monomer such as a body or a polymer containing the monomer as an essential component can be suitably used. As the compound containing a hydroxyl group, for example, polyester-based polyols, polyether-based polyols, acrylic-based polyols, polysiloxane-based polyols, polyurethane-based polyols, and modified polyols thereof can be suitably used. As the isocyanate group-containing compound, for example, a compound obtained by reacting a polyisocyanate (such as isophorone diisocyanate) with the above polyol so as to contain an isocyanate group can be suitably used.

The curable composition may contain an organic solvent such as aromatic hydrocarbons, alcohols, ethers, esters, and ketones, if necessary.

In a powder curable composition using the resin (II),
Examples of the resin (II) having no silanol group include a powder composition containing a powderable resin selected from the other active energy ray-polymerizable unsaturated group-containing resins, and a resin (II) Compounds having a silanol group in the compound capable of being powdered selected from the functional group-containing compounds,
Or a powder composition containing a powderable resin selected from the other active energy ray-polymerizable unsaturated group-containing resins.

Further, as the curable composition in an aqueous solution, for example, a resin (I) and a resin (II) which are made water-soluble by using a water-soluble resin can be used. As the resin which can be made water-soluble, conventionally known resins can be used. Specifically, Japanese Patent Publication No. 52-21526, Japanese Patent Application Laid-Open No. 62-262855,
Unsaturated resins having a cationic or anionic group described in JP-A-4-4671 and JP-A-64-4672 can be preferably used.

In the curable composition of the present invention, when used in combination with other resins and compounds, the colloidal silica (A) component contains 20 to 80% by weight, preferably 20 to 80% by weight, based on the total solids content of the resin and compound. It is desirable to mix at a ratio of 30 to 80% by weight.

If necessary, the curable composition of the present invention may contain a coloring agent, a dispersant, a fluidity modifier, and the like.

The curable composition of the present invention can be cured by irradiating an active energy ray such as an electron beam, an ultraviolet ray, and a visible ray.When the composition is cured by irradiating an ultraviolet ray and a visible ray, the composition contains Photopolymerization initiators (e.g., benzoins, acetophenone, benzophenone, peroxides) and sensitizers (e.g., amines, alkylphosphines, thiols, dyes (xanthone eosin,
Ketocoumarins).

The curable composition of the present invention can be applied to substrates such as wood, paper, inorganic materials, plastics, and metals.

The curable composition of the present invention is a paint, a printing ink, a sealant,
Photoresist, solder resist, plating resist,
It is particularly useful for printing plates, adhesives and the like. In addition, the curable composition of the present invention has high hardness of the film, and has excellent properties of chemical resistance, adhesion, and heat resistance. Therefore, it is particularly preferable to use the curable composition as a sealant, a protective film for electronic parts, and various resist films. .

In addition, an aqueous product of the curable composition of the present invention can be used as, for example, a negative or positive type anionic electrodeposition paint and a negative or positive type cationic electrodeposition paint to obtain a copper foil laminated insulating substrate for printed wiring. .

(Function and Effect of the Invention) The resin composition of the present invention uses a metal chelate or metal alkoxide as a catalyst particularly in the reaction between a silanol group in the colloidal silica (A) component and an alicyclic epoxy group in the compound (B). The two components can be easily bonded to each other, and the polymerizable unsaturated group is introduced into the colloidal silica via the alicyclic epoxy group, resulting in a coating with excellent performance, finish, and transparency. Can be

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” in Examples and Comparative Examples are based on weight.

The above raw materials were mixed and reacted at 100 ° C. for 10 hours with stirring to obtain a solution having a solid content of 33%.

Resin solution A resin having a solid content of 39% was obtained in the same manner as in the resin solution production example except that 3,4 epoxycyclohexylmethyl methacrylate was replaced with glycidyl methacrylate in the resin solution production example.

Resin powder The resin solution was dried at 40 ° C. under reduced pressure to obtain fine powder.

Resin powder The resin solution was dried at 40 ° C. under reduced pressure to obtain fine powder.

Example 1 A resin solution (1150 parts) and α-hydroxyisobutylphenone (15 parts) were mixed, and the resulting mixture was dried on an ABS (acrylonitrile-butadiene-styrene copolymer) plate.
Spray paint to 20μm, heat at 70 ℃ for 10 minutes to remove the solvent, then 30c with 5kw high pressure mercury lamp
Exposure was performed for 30 seconds from a distance of m to obtain a coating. The coating was a continuous coating having no defects such as cracks. Also,
The coating was transparent and had a good pencil hardness (JISK-5400) of 9H.

Comparative Example 1 A coating film was obtained in the same manner as in Example 1, except that the resin solution was used in place of the resin solution. The coating did not form a continuous coating and was left in powder form when the surface was rubbed by hand.

Example 2 A mixture of 1050 parts of a resin solution, 150 parts of trimethylolpropane triacrylate and 20 parts of benzoin ethyl ether was spray-coated on a surface of a zinc-phosphate-treated copper plate so as to have a dry film thickness of 30 μm, and was subjected to spray coating at 70 ° C. for 10 minutes. After heating to remove the solvent, exposure was carried out for 20 seconds from a distance of 50 cm with a 5 kw high-pressure mercury lamp to obtain a coating. The coating was a continuous coating without defects such as cracks. In addition, the coating is transparent, pencil hardness 8H, sticking 100/100 (100 pieces of 1mm square is made on the coating surface with a cutter, and the adhesion of the coating after the cellophane tape is adhered to and suddenly pulled off is checked. The number of remaining squares / the number of squares formed was good.

Comparative Example 2 In Example 2, 1050 parts of the resin solution
A coating was obtained in the same manner as in Example 2 except that the film was replaced with a part. The coating was a film having poor cracking and poor continuity. The coating was opaque and had a bad adhesion of 0/100, and the pencil hardness (the coating peeled off when the coating was scratched with a pencil) was unmeasurable and poor.

Example 3 A mixture of 1200 parts of the resin solution and 12 parts of 2-methyl-1- [4-methylthiophenyl] -2-morpholinopropene was applied and exposed in the same manner as in Example 2 to obtain a coating. . The coating was a continuous coating without defects such as cracks. The coating was transparent and had a good pencil hardness of 7H and a good adhesion of 100/100.

Comparative Example 3 In Example 3, 1200 parts of the resin solution was replaced with silica sol NBA.
A coating was obtained in the same manner as in Example 3, except that the coating was replaced with -1000 parts. The coating was opaque and had a poor adhesion with a 0/100 pencil hardness (coating peeled off) which could not be measured.

Example 4 450 parts of a resin powder, 200 parts of an epoxy acrylic oligomer (2 moles of acrylic acid reacted with 1 mole of Epicoat 828 “manufactured by Shell Chemical Co., Ltd.”), 2-hydroxy-3
-Benzyloxypropyl acrylate; and Disperse 25 parts of the mixture in a ball mill for 6 hours, place it in a 1 cm square mild steel plate mass, and use a 5 kw high-pressure mercury lamp
After exposure for 40 seconds from a distance of cm, the mixture was heated at 140 ° C. for 60 minutes to obtain a cast. 5 hours at 150 ° C and -20 ° C
The thermocycle test was repeated 50 times with a 5-hour thermocycle as one cycle. As a result, there was no change at all before and after the thermocycle test, and the product was good.

Comparative Example 4 A cast was obtained in the same manner as in Example 4, except that the resin powder was replaced with the same portion of the resin powder. The cast material was subjected to a thermocycle test in the same manner as in Example 4, and as a result, cracks occurred in the cast material in 10 cycles.

Example 5 0.1 part of hydroquinone and 288 parts of acrylic acid were added to a resin solution obtained by dissolving 1100 parts of Epicoat E-180S70 (trade name, manufactured by Shell Chemical Co., Ltd., epoxy resin) in 1045 parts of butyl cellosolve. After the reaction was continued until the temperature became below, the mixture was cooled to 70 ° C, and 122 parts of thiodiglycol and 60 parts of acetic acid were added thereto. The reaction was carried out at 70 ° C for 8 hours to obtain a solid containing an acryloyl group and a hydroxyl group. Minute
A 60% resin solution was obtained. Next, 100 parts of the resin solution, the resin solution
150 copies, A mixture of 15 parts and 5 parts of benzoin ethyl ether was applied on a copper foil laminate having through-holes to a dry film thickness of 30 μm, heated at 70 ° C. for 10 minutes to remove the solvent, and then passed through a negative mask. Using an 80 w / cm ultra-high pressure mercury lamp
After exposing with a light amount of 300mj / cm from a distance of 50cm,
After treatment with a developing solution for a certain period of time, the unexposed portion of the film was peeled off, and the remaining film was heated at 140 ° C. for 30 minutes to form a resist film pattern on the copper foil laminate. Table 1 shows the performance effects of the obtained films.

Comparative Example 5 In Example 5, 150 parts of the resin solution was replaced with silica sol IPA.
A resist film pattern was formed in the same manner as in Example 5 except that the resist film was replaced with ST130.

Comparative Example 6 A resist film pattern was formed in the same manner as in Example 6, except that the resin solution was replaced with the same portion as the resin solution.

Table 1 summarizes the performance test results of the films of Comparative Examples 5 and 6.
It was shown to.

[Test Method] Developed: A developer (1.5% Na ₂ CO ₃ aqueous solution) was sprayed onto the exposed resist film at 25 ° C. with a spray pressure of 2 kg / cm ³ for a predetermined time (90 seconds and 180 seconds). .

 ◎ Complete development is possible even in the through hole.

 ○ The substrate surface can be completely developed.

Δ Image defects occur due to erosion and swelling of the substrate surface where development is not possible, or by the developer.

 X Hardly developed.

Dryness to the touch: The film is adhered on the film with a vacuum laminator and exposed. ◎ The film is not contaminated by the coating film at all.

 ○ The film is slightly contaminated by the coating.

× The film is clearly contaminated by the coating. Acid resistance: visually immersed in IN-H ₂ SO ₄ at 60 ° C for 1 hour. ◎ No change in coating state.

 ○ Slight swelling and discoloration are observed in the state of the coating film.

 Δ: Discoloration is clearly observed in the state of the coating film.

 X: The coating film was dissolved or peeled.

Solder plating resistance: In accordance with the test method of JISC-6481, the test piece was floated in a 260 ° C solder bath for 10 seconds as one cycle, and evaluated visually.

Adhesion on eyes after immersion in heat-resistant water: Test piece at 80-90 ° C
For 1 hour in hot water.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 5/00 C09D 5/00 C

Claims (3)

(57) [Claims] 1. A compound having colloidal silica (A) dispersed in an organic solvent and one alicyclic epoxy group in one molecule and one or more active energy ray-polymerizable unsaturated groups in one molecule. An active energy ray-polymerizable unsaturated resin composition obtained by reacting (B) with a metal chelate and / or a metal alkoxide. 2. A powdery active energy ray polymerizable unsaturated resin composition obtained by removing the solvent from the active energy ray polymerizable unsaturated resin composition according to claim 1. 3. An active energy ray-curable composition comprising the active energy ray-polymerizable unsaturated resin composition according to claim 1 or 2 as an essential component.