JPS63260940A - Photoreactive surface treating agent and resin composition - Google Patents

Abstract

PURPOSE:To obtain the title surface-treating agent for modifying the surface of an inorganic substance to improve its affinity for a photocurable resin, mainly consisting of an alkoxytitanium derivative having specified unsaturated carboxylic acid residues as part of substituents. CONSTITUTION:A tetraalkoxytitanium (ai) of formula I [wherein R is a 1-8C linear or branched alkyl such as methyl, ethyl, (iso)propyl, pentyl, n-butyl, n- hexyl or octyl] and/or an alkoxytitanium polymer (aii) of an average degree of condensation <=6, obtained by hydrolytically polycondensing component (i), is reacted with 0.10-0.65mol., per mol. of the alkoxyl groups of component (a), of an unsaturated carboxylic acid (b) of formula II (wherein R' is H-, CH3-, C6H5-, CH3CH=CH-, or C6H5-CH=CH- and R'' is H- or CH3-) at 40-100 deg.C for 1.5-5hr, and the produced alcohol by-product is distilled off to obtain an alkoxytitanium derivative (A) of an average degree of polymerization <=6, containing 35-90%, based on the total substituents, alkoxyl groups and the balance of unsaturated carboxylic acid residues of formula III. Component A is optionally mixed with an organic solvent (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a surface treatment agent, and more specifically, some of the substituents of tetraalcogystitanium and/or its hydrolyzed condensate are unsaturated. An inorganic surface treatment agent mainly composed of alkoxy titanium Eft substituted with a carboxylic acid residue, and a photocurable resin composition containing this surface treatment agent added to a photopolymerizable monomer and/or polymer. Regarding.

The surface treatment agent of the present invention can be used in a composite system with a photocurable polymer MAI-IJ sock inorganic substance, such as a paint, an adhesive, etc., to improve the affinity between the photocurable polymer matrix and the inorganic substance. can improve sex.

Moreover, the photocurable resin composition of the present invention is used as a paint, a resist ink, a coating agent, an adhesive, and the like.

[Conventional technology]

In recent years, in the field of resin thin films such as coatings, inks, coatings, and adhesives, solvent-free photocurable resin compositions have come into widespread use due to social demands such as energy saving and non-pollution. For example, resin compositions made by blending photocurable resins such as acrylate and methacrylate oligomers with photopolymerization initiators, inorganic fillers such as glass beads, and various silane coupling agents are used in printed wiring boards for consumer use. Various resist inks have been proposed for use (
JP-A-61-103968, JP-A-61-098
725, JP-A-60-195171, etc.). In addition, optical fiber coating materials with similar compositions are used as industrial materials, 32. (8), 31 (1984)
A coating composition is disclosed in JP-A-48-028533.

In addition, thermosetting prints are made by blending an inorganic filler such as silicon oxide, a resin curing agent, and a silane coupling agent or titanate coupling agent with a thermosetting resin composition whose main component is an epoxy resin. Resist ink for electroless plating used for wiring boards was published in Japanese Patent Application Laid-Open No. 60-0745.
It is disclosed in Publication No. 99.

[Problem that the invention seeks to solve]

Currently, the field of printed wiring boards in which photo-curable resist inks are used is limited to the field of consumer electronic devices with relatively wide circuit spacing of 200 μm or more, and high-density circuits such as computers and control equipment. It has not yet been adopted in the field of industrial electronic equipment that requires circuit boards. Printed wiring boards for industrial electronic equipment are required to have high electrical insulation properties and resistance to soldering heat under humidified conditions, which are not required for consumer electronic equipment. The reason for this is that the performance of the resist inks currently available is not satisfactory.

In optical glass fiber coatings, adhesion between the glass fibers and the coating is required because gaps between the glass fiber and the coating cause signal loss and noise. Then, adhesion is insufficient. This also applies to paint films.

In addition, in thermosetting resist for electroless plating,
Coupling agents are used to improve the compatibility between inorganic fillers and thermosetting resins, but even when these coupling agents are applied to photocurable resin compositions, they do not have similar properties. It is not possible to obtain a resist film.

The present invention relates to a surface treatment agent that modifies the surface of inorganic substances such as inorganic fillers and optical fibers, and improves the compatibility of these with photocurable resins, and photocurable resins that can be used as resist inks and coating compositions. The object is to provide a composition.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors found that an alkoxytitanium derivative in which a carboxylic acid residue having an unsaturated bond was introduced as a substituent has a large effect of modifying the inorganic surface, and is photosensitive. The present invention was completed based on the discovery that it can be copolymerized with a curable resin to form a strong composite system with an inorganic substance.

In the present invention, 10 to 65% of the substituents are alkoxy groups j-O
R (here, R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms), the remainder being an unsaturated carboxylic acid residue represented by the following general formula: 1l-C=C- COO- (Here, "II, CI+3, CJa
, CH:+Cll=C8- or CJs Cl
1 = Cll-, R'' represents 11- or C113-), and the average degree of condensation is 6 or less. Component A: a photo-radically polymerizable monomer and/or polymer, and Component B: an alkoxytitanium derivative which is the main component of the surface treatment agent. (
Hereinafter, this will be referred to as the "second invention." ).

In the present invention, the alkoxy titanium derivative, which is the main component of the surface treatment agent of the first invention and component B of the photocurable resin composition of the second invention, has the following general formula (11 % formula % (11 where R is a linear or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group.

Ethyl group, propyl group, isopropyl group, normal butyl group, pentyl group, normal hexyl group.

Tetraalkoxytitanium containing one or more types of octyl group, 2-ethylhexyl group, etc. and/or an alkoxytitanium polymer having an average degree of condensation of 6 or less obtained by hydrolytic condensation of these tetraalkoxytitaniums,
Place 1'J! IIs is an alkoxytitanium derivative in which 10 to 65% of the OR group is replaced with a residue of an unsaturated carboxylic acid represented by the following general formula (2) (2) represents C11,-.

More specifically, alkoxytitanium derivatives have the general formula (
an alkoxytitanium monomer derivative in which 1 to 2 of the alkoxy groups (-011 groups) of tetraalkoxytitanium represented by 11 are substituted with residues of an unsaturated carboxylic acid represented by the general formula (2), and Alkoxytitanium polymers with a degree of condensation of tetraalkoxytitanium represented by general formula (1) of 6 or less and 0.10 of the number of alkoxy groups thereof
'f1. These are a mixture of a tanned alkoxytitanium polymer derivative and a heptamer derivative and a polymer derivative.

The alkoxytitanium polymer is produced by hydrolyzing tetraalkoxytitanium represented by the formula -C (+1) using an equimolar amount or less of water in the presence of an acid or alkali catalyst.

゛Alkoxytitanium derivatives include the aforementioned tetraalkoxytitanium, alkoxytitanium polymer, and mixtures thereof, and 0.10 to 0.6 of the total number of alkoxy groups thereof.
and an unsaturated carboxylic acid represented by the general formula (2) in a mole number corresponding to 5, and stirred at a temperature of 40 to 100°C for 1.5 to 5 hours in the presence or absence of a solvent. By holding and reacting, the desired alkoxytitanium derivative can be easily synthesized, and then the desired alkoxytitanium derivative can be produced by distilling off the alcohol by-produced in the reaction at a temperature of 30 to 50° C. under reduced pressure.

These unsaturated carboxylic acids include, for example, C1l
! = CHCOOII, C1l! IcII
= ClIC0OH.

CIh=C(CIli)COOII, 'C112
CII=C(CI!3) COOHlCIl 1cIl
= CIl −C1l = ClIC0O11, CJs
Ctl-CIICOOIll Cill 5clI = CI-Cll ” ClI
C0OH.

etc.

The surface treatment agent of the present invention is an alkoxytitanium derivative obtained by the above method or an organic solvent solution thereof.

The organic solvent is not particularly limited as long as it can dissolve the alkoxytitanium derivative, but when used in a composite system of a photopolymerizable matrix and an inorganic substance, a photopolymerizable nitrate is preferably used. be done. Photopolymerizable nanatsumer
Examples include acrylic acid, methacrylic acid, cyclohexyl acrylate, methylacrylate, benzyl acrylate, 2-ethylhexyl acrylate-1,
Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl methacrylate, styrene, and N-vinylpyrrolidone.

By coating the surface of an inorganic substance, the surface treatment agent of the present invention modifies the surface and improves the compatibility between the inorganic substance and a polymeric substance, particularly a photopolymerizable matrix.

Inorganic substances that can be surface treated include calcium carbonate, titanium oxide, magnesium carbonate, alumina, calcium sulfate, barium sulfate, and iron oxide.

Potassium titanate, talc, kaolin, clay.

Mica, calcium silicate, silica, zeolite.

Glass powder, inorganic fillers added to polymer matrices such as carbon bra, brass powder, iron powder.

Aluminum powder, copper powder, yellow lead, synchromate, molybdate orange, zinc white, chromium oxide green.

Cadmium yellow, cadmium red, lead sulfate.

Examples include inorganic pigments added to paints such as navy blue 2 ultramarine and cobalt violet, inorganic fibers such as glass fibers and optical fibers, and inorganic molded bodies such as ceramic molded bodies and metal molded bodies.

For example, in the case of an inorganic filler blended into a polymer matrix, the alkoxy titanium derivative is preferably 0.1 to 5 parts by weight per 100 parts by weight of the inorganic filler.
Coat 0.5-2.5 parts by weight. Further, as for the surface treatment of a planar inorganic material, it is sufficient to coat the surface to such an extent that a monolayer film of an alkoxy titanium derivative is formed. If the amount of surface treatment agent used for the inorganic substance is too small, the intended surface treatment effect will not be achieved, and even if it is used in excess, the expected effect will not be increased.

There are no particular limitations on the method for surface treatment of inorganic substances as long as the method can uniformly coat the surface of the inorganic substance with a surface treatment agent. For example, a method of immersing an inorganic substance in a surface treatment agent and drying it, a method of spray coating the inorganic substance with a surface treatment agent, a method of adding the surface treatment agent to a polymer matrix in advance and applying it to a composite system with an inorganic substance, A method of adding and mixing a polymer matrix and an inorganic filler to a composite system is adopted.

The second invention is a photocurable resin composition containing, as component A, a photoradically polymerizable monomer and/or polymer, and as component B, an alkoxytitanium derivative which is the main component of the surface treatment agent detailed above.

The photo-radically polymerizable monomer and/or polymer of component A is prepared by irradiating it with active energy rays such as visible light, infrared rays, ultraviolet rays, electron beams, and X-rays in the presence or absence of a photopolymerization initiator. It is a resin matrix that polymerizes and hardens. For example, as a photoradically polymerizable monomer, the compound exemplified as a solvent for the surface treatment agent,
In addition, unsaturated polyester resins and polyol (meth)acrylates are used as photo-radically polymerizable polymers.

Polyester (meth)acrylate, silicone (meth)
Acrylate, polybutadiene (meth)acrylate
Melamine (meth)acrylate, cyclopentadiene (
Examples include resins having an acryloyl group and/or methacryloyl group in the molecule, such as meth)acrylate polyvinyl alcohol (meth)acrylate, and thermoplastic resins such as polyolefin resins that are sensitive to electron beams, X-rays, etc.

The photopolymerization initiator may be one that generates radicals upon irradiation with active energy rays. Typical photopolymerization initiators include benzoin, benzoin methyl ether, and benzoin ethyl ether.

Benzoin isopropyl ether, benzoin isobutyl ether, benzoin acetate, benzophenone, 4-methoxybenzophenone, 4,4''-dimethylbenzophenone, 4-bromobenzophenone.

2.2',4.4'-tetrachlorobenzophenone, 2
-Chloro-4'-methylbenzophenone, 3-methylbenzophenone, 4-t-butylbenzophenone.

Benzyl, benzylic acid, diacetyl, methylene blue,
Acetophenone, 2.2'-jethoxyacetophenone, 9.10-phenanthrenequinone, 2-methylanthraquinone, 2-ethylanthraquinone.

2-t-butylanthraquinone, 1,4-naphthoquinone, diphenyl disulfide F, dithiocarbamate, α
-Chloromethylnaphthalene, anthracene, iron chloride, etc. can be exemplified.

In particular, benzyl dimethyl ketal, 2.2''-jethoxyacetophenone, benzoin isopropyl ether, benzoin isobutyl ether, 2-ethylanthraquinone, etc. are preferably used, and these may be used alone or in combination.
More than one species is used in combination.

The photocurable resin composition of the present invention may contain inorganic substances as fillers or pigments, reactive diluents, Photopolymerization accelerator, stabilizer, adhesion agent, leveling agent, gloss agent, mold inhibitor, defoaming agent,
Anti-skinning agents and the like can be added.

The photocurable resin composition of the present invention is composed of 0.0001 to 10 parts by weight of an alkoxytitanium derivative as component B, and 0.0001 to 10 parts by weight of an alkoxytitanium derivative as component C, based on 100 parts by weight of a polymer matrix consisting of a photoradically polymerizable monomer and/or polymer as component A. The composition contains 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, of a photopolymerization initiator.

The amount of the alkoxy titanium derivative as component B varies greatly depending on the usage of the composition. For example, in the case of ink, paint, etc. containing fillers and pigments, the amount of the alkoxy titanium derivative as component B varies based on 100 parts by weight of the inorganic substance as described above. It is blended in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2.5 parts by weight. In addition, in the case of coating agents, paints, adhesives, etc. that form clear coatings on inorganic molded objects, etc., the amount of the alkoxy titanium derivative as component B is o ,0001 to 0.1 parts by weight, preferably 0.0001 to 0.1 parts by weight.
001-0.05 parts by weight.

The photocurable resin composition of the present invention is suitably used in inorganic coatings, paints, adhesives, etc., and in combination with fillers and pigments, resist inks, paints, etc.

[For production]

The present invention relates to a surface treatment agent for an inorganic substance characterized in that the main component is an alkoxy titanium derivative having an unsaturated carboxylic acid residue as a substituent, and a photo-radically polymerizable polymer matrix containing this alkoxy titanium derivative. This is a photocurable resin composition characterized in that it is blended with.

In alkoxy titanium derivatives, an alkoxy group (-O
R group) is a hydrolyzable reactive substituent that reacts with the 1011 group present on the surface of the inorganic substance to organically bond the inorganic substance and the titanoxane derivative, and also The adhering moisture causes polymerization to form a film having a titanoxane structure.

On the other hand, the unsaturated carboxylic acid residue is a substituent that has an affinity for non-hydrolyzable organic (resin) 7-trisox and has a photoreactive unsaturated double bond in its structure. Therefore, in the polymer 7 trisox before photocuring, the dispersibility of inorganic substances such as fillers and pigments in the resin is
When applied to an inorganic molded body, it improves its wettability. Furthermore, after photocuring, it is cured together with the polymer matrix, improving the adhesion and adhesion between the resin matrix and fillers, pigments, and inorganic surfaces.

Alkoxy group (-OR group) in alkoxy titanium derivative
If there is too little of the alkoxy titanium derivative, that is, if the alkoxy titanium derivative is excessively substituted with unsaturated carboxylic acid residues, it will not only be unstable and easily gel, but also have 10ff groups that are reactive with inorganic substances. Due to the lack of titanoxane, bonding with inorganic substances and formation of a titanoxane structural film are insufficient. On the other hand, if there are too few unsaturated carboxylic acid residues, the affinity and reactivity with the polymer matrix will be insufficient, and the bonding strength between the inorganic substance and the polymer matrix will decrease. Therefore, the alkoxy group (-OR group) in the alkoxy titanium derivative preferably ranges from 35 to 90%.

〔Example〕

The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

In addition, in the following examples, "1 part" and "%" are based on weight unless otherwise specified.

Example 1 Synthesis of alkoxytitanium derivative (3) Sample (
T-1) Add a stirrer, thermometer, air-cooled condenser, and heating device (It!
Add tetraisopropoxy titanium (
284 parts of TPT) and 80 parts of crotonic acid (to TP
T molar ratio -1) was gradually added and heated to 60°C.
After stirring and maintaining for an hour, the pressure was reduced to distill off the by-produced isopropanol, leaving it as a pale yellow and transparent product with a viscosity of 2.5°C at 25°C.
A liquid material (T-1) with 4 voids was obtained.

Infrared absorption vector (IR) of the obtained sample (T-1)
) As a result of analysis, absorption based on unsaturated double bonds was observed. In addition, the ignition residue (as a result of analysis by TiOJ method, T
The i content was 15.5%.

From the above analysis results, it was estimated that sample (T-1) was mainly composed of an alkoxytitanium derivative in which one of the isopropoxy groups of TPT was substituted with a crotonic acid residue.

(t)) Sample (T-2) In the synthesis of sample (T-1), 34 parts and 0 parts of tetra-n-butoxytitanium (TBT) were used instead of TPT, and 224 parts of sorbic acid was used instead of crotonic acid (molar ratio to TBT). -2
) was used, but the reaction and post-treatment were carried out under the same conditions as for sample (T-1), and the viscosity at 25°C was 3.2.
Boies, a pale yellow transparent liquid with a Ti content of 10.8% (
T-2) was obtained.

(C1 sample (T-3) 830 parts of titanoxane isopropoxide (TPT polymer) with an average degree of condensation of TPT of 4 was charged into the same reactor as that used for the synthesis of sample (T-1), and croton acid 4
30 parts (TPT polymer molar ratio to isoproxy groups -0
, 5) was gradually added, heated to 60°C and kept stirring for 3 hours, and the by-product isopropanol was distilled off under reduced pressure.
A pale yellow transparent liquid (T-3) having a viscosity of 162 voids at 5°C was obtained.

As a result of IR analysis of the obtained (T-3), absorption based on unsaturated double bonds and ester bonds was observed, and as a result of analysis using the ignition residue (TiO□) method, the Ti content was 19 It was .8%. From the above analysis results, the sample (T
-3) was estimated to be mainly composed of an alkoxytitanium derivative polymer in which a part of the isopropoxy group of the TPT polymer was substituted with a crotonic acid residue.

(d) Comparative sample (C-1) In the synthesis of sample (T-1), 240 parts of methacrylic acid (molar ratio to TPT = 1) was replaced with 80 parts of crotonic acid (molar ratio to TPT = 1).
Samples (T-1 to TPT molar ratio -3) were used.
The reaction and post-treatment were carried out under the same conditions as in ) to obtain a pale yellow transparent liquid (C-1).

The obtained (C-1) was analyzed under the same conditions as sample (T-1) and was estimated to be isopropoxytitanium tri(methacrylate).

When this (C-1) was stored at 25°C, it gelled after 3 days and could not be used as a surface treatment agent.

Example 2 Coating agent for optical glass fiber la) Synthesis of photopolymerizable resin Bis(4-isocyanatocyclohexyl)methane (hydrogenated MDI) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and an air blowing tube. Hydroxyethyl acrylate (H
EA) 130 parts were added over 2 hours. When the reaction progressed and the temperature rose to about 70°C, stirring was continued for an additional hour while maintaining this temperature to obtain a prepolymer having polymerizable unsaturated bonds.

This prepolymer has a number average molecular weight of 2.800, a hydroxyl group content of 0.80 meq/g, and a tras7s 1.4-bond of 60.
%, hydroxyl group-containing liquid polybutadiene (1,4-PB) with 20% cis 1.4-bonds and 20% 1.2-bonds (trade name: Poly bd-45HT, manufactured by Idemitsu Kosan ■) 300 parts and number average molecular weight 684 and polypropylene glycol (PPG) having a hydroxyl value of 164 was added over a period of 3 hours, and when the temperature reached approximately 70°C, the mixture was stirred and maintained at this temperature for an additional hour to mix the prepolymer and 1.4- P
A mixed resin (photoradical polymerizable polymer matrix) was obtained, which was a mixture of the polymerizable unsaturated bond-containing polybutadiene reacted with B and the polymerizable unsaturated bond-containing polypropylene ether, which is a reaction product of the prepolymer and PPG.

Tb) Preparation of photocurable resin composition Photoradical polymerizable polymer matrix 6 synthesized in the previous section
00 parts, the surface treatment agent/sample synthesized in Example 1 (T-
1) to (T-3) and comparative sample - 5 parts each of proboxythicuntri (isostearate) (C-2) and T-methacryloxypropyltrimethoxysilane (C-3), phenoxyethyl acrylate ( 480 parts of reactive diluent) and N-vinylpyrrolidone (N-V
Add 120 parts of P) and mix well, and then add and mix 36 parts of benzyldimethylkecool (BMK/photopolymerization initiator), filter through a 5 μm filter, and obtain a coating material for optical glass fiber (photocurable resin S). , (2) acid compound) and comparative coating materials (CR-2) and (CR-3) were prepared.

Table 1 shows the viscosity of the resulting coating at 25°C.

(Measurement of physical properties of C1 cured product The coating material prepared in the previous section was applied to a tin plate using a doctor blade to a thickness of 0.1 mm, and then 80 w/a
Distance between lamps is 40cm using metal halide lamps.
It was cured by irradiating it with ultraviolet light for 10 seconds. The obtained cured film was separated by '/jl using the mercury amalgam method to prepare a test sheet.

The following physical properties were measured using the prepared test sheet. The measurement results are shown in Table 1.

Elastic modulus measurement: The elastic modulus was measured in accordance with JIS K-7113.

Heat resistance test: Test sheet 1- was kept in a heat aging tester set at 3Q'C in a nitrogen atmosphere for 10 days and aged.
Further, after being left in a constant temperature room at 20° C. and 50% RH for 24 hours, the elastic modulus was measured.

Dynamic viscoelasticity: Using a dynamic viscoelasticity measuring device (manufactured by Toyo Baldwin 0 Kiku), frequency 35 I (z, heating rate 2°C)
/min, dynamic displacement ±0.025mm, measurement temperature -100℃
It was measured under the conditions of ~+100°C, and the glass transition temperature was determined from the measurement results.

(dl Adhesion Test The coating material prepared in Section Cb1 above was applied to a thickness of Q, lrn rn using a doctor blade on a quartz glass plate, and the distance between the lamps was 40cm using an 80 w/cm metal halide lamp. It was cured by irradiating it with ultraviolet light for 10 seconds.

This coated glass plate was left in a constant temperature room at 20°C x 50% RH for 24 hours, and then immersed in distilled water for 5 days.
A peel test was conducted under the conditions of 10 minutes.

The measurement results are shown in Table 1.

(Left below) (f) Uncoated outer diameter of optical glass fiber 1
The coating material prepared in the FBL section was applied to a 25 μm optical glass fiber so that the outer diameter after coating was 400 μm, and the coated fiber was irradiated with ultraviolet rays using an 80 W/cm metal halide lamp.

The coated fiber obtained using the coating material of the present invention is
No change in transmission loss due to coating was observed, and -50~
The change in transmission loss in the +60°C temperature range is ±0.
It was 05dB/km.

Example 3 Preparation of photocurable resist ink (fa) Preparation of photocurable resist ink 50 parts of acrylic acid adduct of phenol novolac type epoxy resin and trimethylolpropane triacrylate polymer matrix) were added with hydroxypivalic acid ester neopentyl glycoldi. Add and mix 25 parts of acrylate (reactive diluent), and further 5 parts of 2-ethylanthraquinone (photopolymerization initiator) and surface treatment of the surface treatment agent synthesized in Example 1 and the comparative sample used in Example 2. A mixture of 50 parts of talc and 1 part of phthalocyanine green, which had been surface-treated in advance using 0.5 parts of each agent, was added and kneaded through three rolls to form an ultraviolet curable resist ink (photocurable resin composition). ) and comparative inks were prepared.

fbl Resist properties The ink prepared in the previous section was applied to a thickness of 15 μm on a copper-clad laminate, and ultraviolet rays were irradiated for 10 seconds from a distance of approximately 20 V'm using a high-pressure mercury lamp (8 parts W/cm x 3 lamps). It was irradiated and cured.

Using the obtained resist-coated laminate, the following properties were measured. The measurement results are shown in Table 2.

Adhesion: Measured by a cross-cut sellotape peel test.

Heat resistance: Dipped in a 260°C solder bath for 45 seconds and visually observed for peeling, blistering, etc.

Electrical insulation: A DC voltage of 500 V was applied for 1 minute, and the electrical insulation resistance value was measured.

Example 4 White paint ta+ One cycle of paint: Copolymerized methyl acrylate, ethyl acrylate, methyl methacrylate, and N,N'-dimethylaminoethyl methacrylate with a number average molecular weight of 73,000, glass 44 parts of a toluene solution containing 33.5% copolymer (photoradically polymerizable polymer matrix) with a transition point of 5°C, 11 parts of trimethylolpropane trimethacrylate, and the surface treatment agent synthesized in Example 1 and Examples 45 parts of titanium white, which had been surface-treated in advance using 0.45 parts of each of the comparative sample surface treatment agents used in 2, was kneaded using a triple roll to form a paint.

fb) Paint film physical properties Each of the paints prepared in the previous section was coated with an epoxy primer to a thickness of 2 μm and cured by heat. It was coated on a 6 mm thick electrogalvanized steel plate using a bar coater and held in a hot air oven at 130° C. for 3 minutes to volatilize the solvent.

Then, using an ICT electron beam accelerator with a voltage of 300 KV and a current of 65 mA, a 2 M rad electron beam was irradiated in a nitrogen atmosphere to cure the coating film.

Regarding the cured coating film, coating film properties and other coating film properties based on the following JIS K-5400 were measured.

The measurement results are shown in Table 3.

Pencil hardness: Paint film breaking hardness adhesion at a load of 1 kg
Properties: Vertical Cellotape peel test Flexibility: Center rod diameter with no abnormality observed at bending angle of 180 degrees Impact strength: Height with no abnormality observed on coating at a load of 500gxl/2' Alkali resistance: Soak in 5%~A01 aqueous solution (room temperature) for one week? ? Appearance after 1 Acid resistance: 5% 11□SO, 1 in aqueous solution (normal IjL)
Appearance salt water resistance after immersion for one week: Time required for one side 211 separation to reach 3 rnm (based on JIs J-2371) Weather resistance: Accelerated weather resistance test was conducted, and the coating surface was touched with the finger after 500 hours. The presence or absence of chalking was examined.

〔Effect of the invention〕

As shown in Example 1, an alkoxytitanium derivative (comparative sample (C
-1)) gels in a short period of time and cannot be used as a surface treatment agent, whereas the surface treatment agent of the present invention when added to an optical glass fiber coating (see Example 2)
It improves water resistance without reducing its elastic modulus or heat resistance, and when added to photocurable resist ink (see Example 3), it improves its adhesion and electrical insulation. Also, when added to white thread paint (see Example 4)
It improves most coating film properties, including adhesion and bending resistance. In contrast, isopropoxytitanium tri(isostearate) (comparative sample (C-2)) and γ-methacryloxypropyltrimethoxysilane (comparative sample (C-3)), which have been conventionally used as surface treatment agents.
Although there are some items where the effect of the addition is recognized, no overall effect of the addition is observed.

That is, these effects are that the surface of the inorganic substance is modified by prior surface treatment with the surface treatment agent of the present invention or its addition to the resin system, and the compatibility between the photopolymerizable resin and the inorganic substance is improved; When the unsaturated double bonds of the alkoxy titanium derivative, which is the main component of the surface treatment agent, copolymerize with the photopolymerizable resin, the inorganic substance and the photopolymerizable polymer matrix organically bond and develop. do.

Therefore, the photocurable resin composition containing the surface treatment agent of the present invention (second invention) can be used in fields where it is applied to the interface between an inorganic substance and a photopolymerizable resin, such as optical glass fiber coatings and fillers. It can be suitably used in resist inks containing pigments, paints containing pigments, adhesives between other inorganic materials and transparent materials, and the like.

The present invention provides a surface treatment agent (first invention) that modifies the surface of an inorganic substance to improve its compatibility with a photopolymerizable resin, and a photocurable resin composition containing this surface treatment agent (second invention). The industrial significance of this is extremely large.

Claims (2)

[Claims] (1) 35-90% of the substituents are alkoxy groups: -OR(
Here, R represents a straight chain or branched alkyl group having 1 to 8 carbon atoms. ), and the remainder is an unsaturated carboxylic acid residue represented by the following general formula: ▲Mathematical formulas, chemical formulas, tables, etc.▼ (Here, R' is H-, CH_3-, C_H_5-,
CH_3CH=CH- or C_6H_5-CH=CH
-, R'' represents H- or CH_3-), and the average degree of condensation is 6 or less. (2) Component A: photoradically polymerizable monomer and/or polymer, and component B: 35 to 90% of the substituents are alkoxy groups: -OR (here, R is a straight chain or branched chain having 1 to 8 carbon atoms). (represents an alkyl group with branches), unsaturated carboxylic acid residue whose remainder is represented by the following general formula: ▲Mathical formula, chemical formula, table, etc.▼ (Here, R' is H-, CH_3-, C_6H_5-
, CH_3CH=CH- or C_6H_5-CH=C
A photocurable resin composition containing an alkoxytitanium derivative having an average degree of condensation of 6 or less, where H- represents H- or CH_3-.