JPH03237113A - Unsaturated resin composition polymerizable by active energy ray and curable composition containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition having excellent curability and giving a coating film having excellent mechanical properties, etc., by reacting colloidal silica dispersed in an organic solvent and a compound containing an alicyclic epoxy group and an unsaturated group polymerizable with active energy rays in the presence of metallic chelate, etc. CONSTITUTION:Colloidal silica (preferably having 0.005-0.1mum average particle diameter) dispersed in an organic solvent (e.g. methyl alcohol) is reacted with a compound having an alicyclic epoxy group and at least an unsaturated group polymerizable by active energy rays [e.g. a compound expressed by the formula (R1 is H or methyl; R2 is 1-6C bifunctional aliphatic saturated hydrocarbon group)] in the presence of a metallic chelate (e.g. diisopropoxyethyl acetoacetatealuminum) and/or metallic alkoxide (e.g. aluminum triisopropoxide) to afford the aimed resin composition. Furthermore, said composition is mixed with another composition to afford a curable composition suitable for coating material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) 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.6 The inorganic filler is used to obtain a photocured film with excellent physical properties such as hardness and heat resistance. It is blended in large amounts. However, in this composition, the light transmittance is reduced by the inorganic filler, so the curability of the film is poor, and the film is brittle and porous, resulting in poor mechanical properties, water resistance, adhesion, and chemical resistance. It had the disadvantage of being inferior.

(Means for Solving the Problems) As a result of extensive research in order to solve the above problems, the present inventors have developed a compound having colloidal silica, an alicyclic epoxy group, and an active energy ray polymerizable unsaturated group. When these are reacted in the presence of a metal chelate and/or metal alkoxide, the reaction between the silanol group and the alicyclic epoxy group in the colloidal silica component can be easily carried out, and the curing obtained using this 6. The present inventors have discovered that the composition has excellent curing properties by active energy stripe irradiation, and that the formed film has excellent mechanical properties, water resistance, chemical resistance, adhesion, etc., and has thus completed the present invention. .

That is, the present invention provides a compound having colloidal silica (A) dispersed in an organic solvent, one alicyclic epoxy group in one molecule, and one or more active energy ray polymerizable unsaturated groups in one molecule. (B) in the presence of a metal chelate and/or metal alkoxide (hereinafter referred to as "metal compound (C)"). ``Resin (I)''), and a powdered active energy ray polymerizable unsaturated resin composition obtained by removing the solvent (hereinafter referred to as ``Resin (I)'').
This invention relates to active energy pure curable compositions containing resin (II) J) and these resin compositions as essential components.

The colloidal silica (A) used in the resin (1) of the present invention has an average particle diameter of 0.005P-0,l/
III can be used.

If the average particle size is larger than about 0.1P, there is a risk that the cured product will become cloudy or the sedimentation stability will decrease.On the other hand, if the average particle size is smaller than about 0.005F, the viscosity of the composition will be high. The organic solvent, which is not preferred because it becomes difficult to handle, can be used without any particular restriction as long as it can stably disperse silica. Preferred specific examples include methyl alcohol, ethyl alcohol, n
-propyl alcohol, 1so-propyl alcohol,
n-butyl alcohol, 1so-butyl alcohol, 5
Cl-a monohydric alcohols such as ec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, n-hebutyl alcohol: ethylene glycol, diethylene glycol, propylene glycol,
polyhydric alcohols such as dipropylene glycol,
: Ethers such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; Amides such as N,N-dimethylformamide; Nitriles such as acetonitrile. In addition, six combinations of organic solvents other than those mentioned above, such as aromatic hydrocarbons, esters, and ketones, can be used.

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-memberable unsaturated groups in one molecule. The active energy-polymerizable unsaturated group can be selected and used without particular limitation as long as it is activated by active energy rays such as visible light, ultraviolet rays, and electron beams and causes a polymerization reaction. Specifically, vinyl groups, allyl groups, (meth)acryloyl groups, (
Examples include meth)acrylamide group.

Representative examples of compound (B) include those listed below.

10 11 [In each general formula, R' represents a hydrogen atom or a methyl group. R
2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. R3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. m
represents an integer of 1 to 10.] In the above, 2 having 1 to 6 carbon atoms represented by R2
Examples of aliphatic saturated hydrocarbon groups include linear or branched alkylene groups such as methylene, ethylene, propylene,
Examples include tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R3 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, and phenylene.

As the above-mentioned compound (B), it is not preferable to use a compound having two or more alicyclic epoxy groups in one molecule because it will cause viscosity or gelation.
When a polymerizable unsaturated group-containing compound having H-CH,,\1 group is used, the reactivity between the epoxy group and the silanol group in the colloidal silica component is poor, so the colloidal silica component and the unsaturated group-containing compound component are Since the bonding is insufficient, a cured film with excellent appearance and performance cannot be obtained.

Colloidal silica (A) and compound (B) can be blended as appropriate depending on the required film performance, but usually the total solid content of both is 80 to 20% by weight of colloidal silica (A),
Preferably 80-30% by weight, compound (B) 20-80%
The blending ratio is 20 to 70% by weight, preferably 20 to 70% by weight. If colloidal silica (A) is less than 20% by weight and compound (B) is more than 80% by weight, coating performance such as hardness and heat resistance will be insufficient; on the other hand, colloidal silica (A)
is more than 80% by weight and the amount of compound (B) is less than 20% by weight, which is not preferable because cracks may occur in the film or transparency may be poor.

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 61 types of aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds can be used. As a metal chelate compound, for example, JP-A-1-129060
You can use the one after the number. Specifically, diisopropoxy ethylacetoacetate aluminum, tris(ethylacetoacetate) aluminum, isopropoxy
Bis(ethylacetoacetate)aluminum, monoacetylacetonate bis(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)
Aluminum, tris(isopropylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, monoethylacetoacetate bis(
acetylacetonato)aluminum, tris(acetylacetonato)aluminum, tris(propionyl acetonato)aluminum, acetylacetonato bis(propionyl acetonato)aluminum, diisopropoxy bis(ethylacetoacedate) titanium, diisopropoxy Preferred examples include bis(acetylacetonato)titanium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, and tetrakis(ethylacetoacetate)zirconium.

Metal alkoxides include aluminum, titanium, zirconium, sodium, potassium, calcium,
Metals such as lithium have an alkoxy group, preferably C3
~I8 Compounds to which an alkoxy group is bonded can be used. These compounds may be associated, specifically aluminum triisopropoxide, aluminum tri-5e
C-butoxide, aluminum tri-n-butoxide,
titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide,
Titanium tetra-tert-butoxide, zirconium tetraisopropoxide, zirconium tetra-n-
Preferred examples include propoxide, zirconium tetraisobutoxide, zirconium tetra-n-butoxide, and zirconium tetra-tert-butoxide.

The metal compound (C) is 0.0 parts by weight based on 100 parts by weight of the total solid content of colloidal silica (A) and compound (B).
It is blended in an amount of 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

by continuing heating at a reaction temperature of about 40-130° C. for about 1 to 10 hours.

Colloidal silica (A
) component may or may not contain silanol groups.

Furthermore, the resin (II) of the present invention can be used as a powdered resin composition by removing the solvent from the composition containing the organic solvent.

The curable composition of the present invention is characterized in that the resin (I) and/or the resin (
II) as an essential component, and can be used alone or in combination with others such as the following curable composition. Further, these materials may be in any form, such as solutions in water or organic solvents, or powders.

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

In the curable composition of an organic solution using resin (I), those having no silanol group in the resin (1),
Other active energy ray polymerizable unsaturated group-containing resins other than those mentioned above, at least one type of active energy ray polymerizable unsaturated group containing monomers, or resins (
1) Those having a silanol group in them are compounds containing a functional group having a functional group that reacts with the silanol group, or compounds containing the above-mentioned other active energy ray polymerizable unsaturated group-containing resins and/or monomers. can be used.

As other resins, six conventionally known resins can be appropriately selected and used. Specifically, epoxy acrylic oligomers, polyester oligomers, urethane acrylic oligomers, acrylic oligomers, oligoester acrylic oligomers, ether acrylic oligomers,
Oligomers such as book diene oligomers and spiran ring-containing acrylic oligomers can be suitably used. The latter have an average of one or more active energy cotton polymerizable unsaturated groups in one molecule and have a molecular weight of 100 to 20,000.

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

The above-mentioned functional group-containing compound has at least one functional group selected from epoxy groups, silanol groups, hydrolyzable groups directly bonded to silicon, hydroxyl groups, incyanate groups, etc. that reacts with silanol groups in one molecule. at least 61
It has more than one. When this compound is used, the curing reaction due to active energy ray irradiation and the curing reaction due to heating occur simultaneously, resulting in the effect of improving coating film performance.

As the above-mentioned functional group-containing compound, conventionally known compounds can be appropriately selected and used. Specifically, examples of the compound having an epoxy group include compounds such as, homopolymers of the compound (B) or other monomers [for example (meth)
A copolymer with the monofunctional monomer 1 excluding acrylic acid,
Alicyclic epoxy compounds such as Chinnox 201 and Chinnox 206 (all products of Chisso Corporation, alicyclic epoxy resins) can be suitably used. In addition to the above, aliphatic epoxy group-containing compounds that do not have an alicyclic epoxy group can be used, but alicyclic epoxy group-containing compounds have inferior reactivity compared to alicyclic epoxy group-containing compounds. 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.) that is preferably used in combination with a silanol group and/or an alkoxysilane group Specifically, it is disclosed in JP-A-62-197423.
Polysiloxane-based macromonomers described in JP-A-63-108049, alkoxysilane group-containing vinyl monomers described in JP-A-63-108049, etc. are monomers that contain these monomers as an essential component. It can be used suitably. As the compound containing a hydroxyl group, for example, polyester polyols, polyether polyols, acrylic polyols, polysiloxane polyols, polyurethane polyols, and modified polyols thereof can be suitably used. The isocyanate group-containing compound can be suitably used, for example, by reacting the polyol with a polyisocyanate (such as isophorone diisocyanate) so as to contain an isocyanate group.

In addition, the above curable composition may contain an organic solvent,
For example, aromatic hydrocarbons, alcohols, ethers,
It can contain things such as esters and ketones.

In the powder curable composition using resin (II),
For those having no silanol group in the resin (II), a powder composition containing a powderable resin selected from the other active energy ray polymerizable unsaturated group-containing resins,
Moreover, in 6 having a silanol group in the resin (II),
This is a powder composition containing a powderable compound selected from the functional group-containing compounds, or a powderable resin selected from the other active energy ray polymerizable unsaturated group-containing resins.

Furthermore, in the curable composition of an aqueous solution, for example, a resin (
I) and resin (II) can be made water-based using a resin that can be made water-based. As the resin that can be water-based, conventionally known resins can be used. Specifically, Japanese Patent Publication No. 52-21526, Japanese Patent Publication No. 62-262855
No. 1, JP-A-64-4671, JP-A-64-4
Unsaturated resins having a cationic or anionic group as described in Japanese Patent No. 672 and the like can be suitably used.

In the curable composition of the present invention, when used in combination with other resins and compounds, colloidal silica C'
It is desirable that component A) be blended in an amount of 20 to 80% by weight, preferably 30 to 80% by weight, based on the total solid content of the resin and compound.

The curable composition of the present invention may contain colorants, dispersants,
Things such as fluidity modifiers can be added.

The curable composition of the present invention can be cured by irradiation with active energy rays such as electron beams, ultraviolet rays, and visible light. A photopolymerization initiator (for example, benzoins, acetophenone, benzophenone, peroxides) and a sensitizer (for example, amines, alkyl phosphines, thiols, and dyes (xanthone eosin, ketocoumarins, etc.) are added to the mixture.

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

The curable composition of the present invention is particularly useful for paints, printing inks, sealants, photoresists, solder resists, plating resists, printing plate materials, adhesives, and the like. In addition, the curable composition of the present invention has a high coating hardness and excellent chemical resistance, adhesion, and heat resistance, so it is particularly desirable to use it as a sealant, a protective coating for electronic components, and various resist coatings. .

Further, the aqueous version of the curable composition of the present invention can be used as, for example, a negative or positive anionic electrodeposition paint or a negative or positive cationic electronic sign paint to obtain a steel foil laminated insulating substrate for printed wiring, etc. .

(Actions and Effects of the Invention) The resin composition of the present invention uses a metal chelate or a metal alkoxide as a catalyst, particularly in the reaction between the silanol group in the colloidal silica (A) component and the alicyclic epoxy group in the compound (B). This allows for easy bonding of surrounding components, and the easily polymerizable unsaturated groups are introduced into colloidal silica via alicyclic epoxy groups, resulting in a coating with excellent performance, finish, and transparency. can get.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

"Part j" and "%" in Examples and Comparative Examples are based on weight.

Example of Preparation of Resin Solution Methyl methacrylate Methoxyhydroquinone 0.04 part The above raw materials were mixed and reacted at 110'C for 6 hours with stirring to obtain a solution with a solid content of 39%.

Resin solution ■Production example Solid content 20%) 3.4 Epoxycyclohexyl 50 parts Methyl acrylate tetrakis (ethyl acetoacetate 1 part Tonato)
Zirconium hydroquinone 0.01 part The above raw materials were mixed and reacted at 90° C. for 8 hours with stirring to obtain a solution with a solid content of 24%.

Resin solution ■Production example Solid content 20%) aluminum) Hydroquinone 0.01 part The above raw materials were mixed and reacted at loo'c for 10 hours with stirring.
A solution with a solids content of 33% was obtained.

Resin Solution ■ A solution with a solid content of 39% was produced using the same formulation and method as in the Resin Solution ■ Production Example, except that 3.4 epoxycyclohexyl methyl methacrylate was partially replaced with glycidyl meccrylate in the Resin Solution Production Example. I got it.

Resin Powder (2) The resin solution was dried under reduced pressure at 40°C to obtain a fine powder.

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

Example 1 1,150 parts of the resin solution (1) and 15 parts of α-hydroxyisobutylphenone were mixed, and the mixture was spray-coated onto ABS (acrylonitrile-butadiene) sea urchin and heated at 70'C for 10 minutes to remove the solvent. After that,
A coating was obtained by exposure for 30 seconds from a distance of 30 cm using a 5 parts w high pressure mercury lamp. The film was a continuous film with no defects such as cracks. Further, the film was transparent and had a good pencil hardness (JISK-5400) of 9H.

Comparative Example 1 A coating was obtained in the same manner as in Example 1, except that the same amount of resin solution (2) was used instead of the resin solution in Example 1. The film did not form a continuous film and remained in powder form when the surface was rubbed by hand.

Example 2 Resin solution ■l 050 parts, trimethylolpropane triacrylate 150 parts and benzoin ethyl ether 2
0 parts of the mixture was spray-painted on the surface of a zinc phosphate-treated copper plate to a dry film thickness of 30/III and heated at 70°C.
After heating for 10 minutes to remove the solvent, the film was exposed to light from a distance of 50 cm for 20 seconds using a 5 parts W high pressure mercury lamp to obtain a film. The coating was a continuous coating without defects such as cracks. In addition, the film is transparent, has a pencil hardness of 8H, and has a goban area [100/100 (1 mm
100 squares were made, cellophane tape was applied closely to the squares, and then rapidly pulled off, and the state of adhesion of the film was observed. The number of remaining squares was 7 (the number of squares created), which was good.

Comparative Example 2 In Example 2, 1050 parts of resin solution ■ was replaced with resin solution ■1
A coating was obtained in the same manner as in Example 2 except that 150 parts were used. The film had fine cracks and poor continuity. In addition, the film is opaque and has a density of 0/1.
00, pencil hardness (the coating peeled off when scratched with a pencil) was unmeasurable and poor.

Example 3 A mixture of 1200 parts of resin solution (1) 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 film. Ta. The coating was a continuous coating without defects such as cracks. In addition, the coating is transparent and has a pencil hardness of 7H.
It was good with a goban area weight of 1100/100.

Comparative Example 3 A coating was obtained in the same manner as in Example 3, except that 200 parts of the resin solution (1) was replaced with 1000 parts of silica sol NBA-ST. The film is opaque and has a rough weight.
O/100 pencil hardness (coating peeled off) was unmeasurable and poor.

Example 4 450 parts of resin powder, 200 parts of epoxy acrylic onogomer (Epicote 828, manufactured by Ciel Chemical Co., Ltd., in which 2 moles of acrylic acid was reacted with 1 mole), 2-hydroxy-3-benzyloxyprobyl. 6, which had been dispersed with acrylate and a mill for 6 hours, was placed in a mild steel plate square measuring 1 cm on each side, exposed to light for 40 seconds from a distance of 30 cm using a 5-part high-pressure mercury lamp, and then heated at 140°C for 60 minutes. A cast product was obtained.The cast product was heated at 150°C.

A thermocycle test was repeated 50 times, with one cycle being a thermocycle of 5 hours and -20°C for 5 hours. The results were good with no change at all before and after the thermocycle test.

Comparative Example 4 A cast product was obtained in the same manner as in Example 4, except that the resin powder (2) in Example 4 was replaced with resin powder (2). The cast product was subjected to a thermocycle test in the same manner as in Example 4, and as a result, cracks appeared in the cast product after 10 cycles.

Example 5 Epicote E-180370 (trade name: Shell Chemical Co., Ltd.,
epoxy resin) 1100 parts butyl cellosolve 1045
0.1 part of hydroquinone and 288 parts of acrylic acid were added to the resin solution dissolved in 100% of the resin solution, heated to 100°C, continued the reaction until the acid value became 5 or less, cooled to 70"C, and further added thio 122 parts of diglycol, 60 parts of acetic acid
1 and reacted at 70°C for 8 hours to obtain a 60% solids resin solution containing acryloyl groups and hydroxyl groups.
Next, a mixture of 100 parts of the resin solution and 5 parts of benzoin ethyl ether was applied onto a copper foil laminate having a through-hole to a dry film thickness of 30P, and heated to 70°C for 1
After heating for 0 minutes to remove the solvent, it was exposed through a negative mask to an 80 W/cm ultra-high pressure mercury lamp from a distance of 50 cm at a light intensity of 300 mj/cm, and then treated with a developer for a certain period of time. After peeling off the coating in the unexposed areas, the remaining coating was heated at 140° C. for 30 minutes to form a resist film pattern on the copper foil laminate. The performance results of the obtained membrane are shown in Table 1.

Comparative Example 5 In Example 5, 150 parts of the resin solution was added to Silica Sol I.
A resist film pattern was formed in the same manner as in Example 5 except that 130 parts of PA-5T was used.

Comparative Example 6 A resist film pattern was formed in the same manner as in Example 6 except that in Example 5, the resin solution (2) was partially replaced with the resin solution (2).

The performance test results of the membranes of Comparative Examples 5 and 6 are summarized in Table-1.

Table 1 [Test method] Developability: Developing solution (1.5% Nag C0w aqueous solution)
It is possible to completely develop the inside of 0-through holes by spraying on the exposed resist film at 5° C. and a spray pressure of 2 kg/c for a predetermined period of time (90 seconds and 180 seconds).

○The substrate surface can be completely developed.

△ Image defects also occur on the substrate surface due to areas that cannot be developed or due to erosion or swelling caused by the developer.

× is almost never developed.

Dry to the touch After the film is adhered to the film using a vacuum laminator and exposed, the O film is not contaminated by the coating at all.

○The film is slightly contaminated by the paint film.

*Acid resistance in which the film is clearly contaminated by the coating film: IN After immersion in H2SO+ at 60°C for 1 hour, visual inspection shows no change in the state of the coating film.

○ Slight swelling or discoloration of the paint film is observed.

△Appearance of obvious discoloration of the coating film.

×The paint film is melted or soldered.

Resistance to solder plating: Solder the test piece at 260°C according to the test method of JISC-6481. One cycle is 10 seconds of floating in the valley, and visually evaluated.

Grid adhesion after immersion in heat-resistant water: test beads 80-9
It was immersed in hot water at 0°C for 1 hour.

Claims (3)

[Claims] (1) Colloidal silica (A) dispersed in an organic solvent, one alicyclic epoxy group in one molecule and one alicyclic epoxy group in one molecule.
An active energy ray polymerizable unsaturated resin composition obtained by reacting a compound (B) having at least one active energy ray polymerizable unsaturated group in the presence of 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 item 1. (3) An active energy ray-curable composition containing the active energy ray polymerizable unsaturated resin composition described in Items 1 and 2 as an essential component.