JP2000212443A - Photo-cationically curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which gives a cured product excellent in water- and oil-repellent properties, stain resistance and hardness by composing it from a condensate of a hydrolyzate of an organic functional group-containing Si compound having an epoxy group or an oxetanyl group with a hydrolyzate of an organic functional group-containing Si compound having a fluoroalkyl group. SOLUTION: This composition comprises a condensate of hydrolyzate of a compound having a structure represented by formula I and a hydrolyzate of a compound having a structure represented by formula II. In the formulae, R0 is an organic functional group bearing an epoxy group or an oxetanyl group, desirably an organic functional group represented by formula III; X is a hydrolyable group, desirably a (cyclo)alkoxy or aryloxy; R1 is an organic functional group bearing a fluoroalkyl, desirably an organic functional group represented by formula IV; R8 is H or a 1-6C alkyl; R9 is a 2-6C alkylene; R2 is a 1-4C alkylene; and m is 0-10. Preferably, the hydrolyzate condensate further comprises as a constituent a reactive silicone bearing at least one siloxane bond-forming group in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationically photocurable resin composition used as a coating agent for electronic parts and the like, and more particularly to a cationically photocurable resin composition having a cationically photopolymerizable functional group and having a fluoroalkyl group introduced therein. The present invention relates to a resin composition comprising a condensate of a hydrolyzate of a silicon compound thus obtained. Since the cured product formed from the photocationic curable resin composition of the present invention has a fluoroalkyl group, it is useful as, for example, a stain-resistant paint or a coating material for preventing graffiti.

[0002]

2. Description of the Related Art In the field of photocuring, polyfunctional acrylates and unsaturated polyesters are widely used as materials to be used, and photoradical polymerization is widely studied as a curing method.
It is also used industrially.

However, there is a problem that photoradical polymerization is inhibited by oxygen. In particular, when the coating composition is cured by radical polymerization in an air atmosphere, as the composition becomes thinner, the effect of polymerization inhibition by oxygen becomes more remarkable, and it is not possible to cure the composition quickly and completely. There is a restriction that it must be cured in an active atmosphere.

On the other hand, photocationic polymerization is not affected by polymerization inhibition by oxygen unlike photoradical polymerization,
It has the feature that polymerization can be completely advanced even in air. In particular, a composition comprising an epoxy compound or an oxetane compound having a silicone chain has good curability even in air, and the cured product has good heat resistance and chemical resistance, excellent adhesive strength, and good stain resistance. As this type of technology, for example, Japanese Patent Laid-Open No.
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a compound having an oxetanyl group introduced into both ends of silicone.

[0005]

However, a cured product of the above cationic photocurable composition comprising an epoxy compound or an oxetane compound having a silicone chain has a basic skeletal structure composed of silicone or polyether. There is a problem that the surface hardness generally tends to be insufficient when used as a coating agent.

The present inventors have previously found that the use of a silsesquioxane compound having an oxetanyl group as a photocurable compound improves the surface hardness of the resulting cured product.

However, the cured film of this composition has insufficient properties such as stain resistance and water / oil repellency depending on the use. As a method for improving this point, it is conceivable to mix a silicone compound with this composition. However, since the photocurable compound has poor compatibility with silicone, a composition obtained by simply mixing a silicone compound with this compound is considered. The product is liable to cause problems such as non-uniformity, repelling at the time of application, or bleeding of the silicone compound from the cured product. Therefore, the coating film formed from the composition,
There is a problem that high hardness, excellent water / oil repellency, and stain resistance cannot be sufficiently exhibited.

The present invention has been made by focusing on the problems existing in the prior art as described above. An object of the present invention is to provide a cationic photocurable resin composition which is excellent in water / oil repellency and stain resistance and can obtain a cured product such as a coating film having high hardness.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention.

That is, the cationic photocurable resin composition of the first invention in the present invention is represented by a compound represented by the following formula (I) and a compound represented by the following formula (II): And a condensate of both hydrolysates of the above compound.

[0011]

Embedded image (However, R ⁰ is an organic functional group having an epoxy group or an oxetanyl group, and X is a hydrolyzable group.)

[0012]

Embedded image (However, R ¹ is an organic functional group having a fluoroalkyl group, and X is a hydrolyzable group.) In the second invention, the condensate of the hydrolyzate in the first invention is one molecule. And a reactive cationic silicone having at least one siloxane bond-forming group as a component.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. In the present specification, a compound having an oxetanyl group is referred to as an “oxetane compound”.

The cationic photocurable resin composition is represented by a compound represented by the following formula (I) (hereinafter, referred to as compound (I)) and a structural formula represented by the following formula (II). (Hereinafter, referred to as compound (II)) in the form of a hydrolysis product and a condensation product of a hydrolyzate obtained by a condensation reaction.

[0015]

Embedded image (However, R ⁰ is an organic functional group having an epoxy group or an oxetanyl group, and X is a hydrolyzable group.)

[0016]

Embedded image (However, R ¹ is an organic functional group having a fluoroalkyl group, and X is a hydrolyzable group.) The compounds (I) and (II) will be described in detail below. (1) R ⁰ in the above formula (I) for the compound (I)
Is an organic functional group having an epoxy group or an oxetanyl group, and is preferably an organic functional group having an oxetanyl group. This is because the photopolymerization rate of the oxetanyl group is higher than that of the epoxy group. In particular, the compound (1) in which R ⁰ has an oxetanyl group is suitably used for applications requiring rapid photocurability, such as when coating on paper or plastic. In addition, the compound (I) having an oxetanyl group has a larger molecular weight due to photocuring than the compound having an epoxy group, and thus various physical properties tend to be better.

In the present invention, particularly preferred R ⁰ is an organic functional group represented by the following structural formula (VI).

[0018]

Embedded image In the formula (VI), R ⁸ is a hydrogen atom or a group having 1 to 1 carbon atoms.
And particularly preferably an ethyl group. R ⁹ is an alkylene group having 2 to 6 carbon atoms, particularly preferably a propylene group. this is,
This is because it is easy to obtain or synthesize an oxetane compound that forms such an organic functional group. If the carbon number of R ⁸ or R ⁹ in the formula (VI) exceeds 7, the surface hardness of the cured product becomes insufficient, which may be undesirable depending on the use.

The hydrolyzable group X in the above formula (I) is
The group is not particularly limited as long as it has a hydrolyzable group, and examples thereof include a halogen atom, an alkoxy group, a cycloalkoxy group, and an aryloxy group. Further, one molecule of this compound contains three X's, and these may be all the same group or two or more different groups. The hydrolyzable group X is preferably an alkoxy group, a cycloalkoxy group or an aryloxy group. The reason is that when X is a halogen atom, hydrogen halide is generated by hydrolysis, so that the reaction system is likely to be in an acidic atmosphere, and therefore, an epoxy group or an oxetanyl group (hereinafter, referred to as an "oxygen group").
Also referred to as "oxetanyl group and the like." ) May open the ring.

The above "alkoxy group" includes, for example, methoxy group, ethoxy group, n- and i-propoxy group,
-, I- and t-butoxy groups. Also,
Examples of the “cycloalkoxy group” include a cyclohexyloxy group and the like, and examples of the “aryloxy group” include a phenyloxy group and the like. Among them, X has 1 to 1 carbon atoms.
Compound (I), which is an alkoxy group of No. 3, is preferable because of good hydrolyzability. Compound (I) in which X is an ethoxy group is particularly preferred because the raw materials are easily available, the hydrolysis reaction is easily controlled, and the toxicity is low. (2) R ¹ in the formula (II) for the compound (II)
Is an organic functional group having a fluoroalkyl group. As R ¹ , an organic functional group represented by the structural formula shown in the following formula (III) is preferable because the production of the compound (II) is simple and the compound is easily available.

[0021]

Embedded image (However, m is an integer of 0 to 10, and R ² has 1 to 1 carbon atoms.
4 alkylene group. In addition, X in the formula (II) is the same as the hydrolyzable group in the formula (I).

The compound (I) and the compound (II) are used in an amount of 20 to 95% by weight of the compound (I) and the compound (I).
It is desirable that I) is 80 to 5% by weight. When the amount of the compound (I) is less than 20% by weight, physical properties such as hardness of the obtained cured product tend to decrease. On the other hand, compound (I)
Exceeds 95% by weight, the water- and oil-repellency and stain resistance of the resulting cured product are liable to decrease.

The condensate of the hydrolyzate of both the compound (I) and the compound (II) also has, as a constituent, a reactive silicone having one or more siloxane bond-forming groups in one molecule. The case is preferable because the weather resistance and the water / oil repellency are particularly good. (3) Reactive silicone As reactive silicone, one or more “siloxane bond forming groups” in one molecule
Any compound can be used without particular limitation. The reactive silicone is preferably a linear or branched linear silicone, and may have a siloxane bond-forming group described later on its side chain or at its terminal.

As the reactive silicone, it is preferable to use at least one selected from the compounds represented by the structural formulas represented by the following formulas (IV) and (V).

[0025]

Embedded image

[0026]

Embedded image Here, X ′ is a siloxane bond forming group, and R ³ and R ⁶ are substituents selected from an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group and an aryl group, respectively. Formulas (IV) and (V) above
Two R ³ contained in the compound in one molecule shown in may be the same groups or may be different groups. This is R ⁶
The same applies to.

R ⁴ and R ⁵ are each an alkyl group,
It is a cycloalkyl group or an aryl group. R ⁴ and R ⁵ may be the same group or different groups. Further, may be an n-number of R ⁴ are different even in two or more be all the same radical groups contained in one molecule is the same for R ^5.

R ⁷ is an alkyl group, a cycloalkyl group or an aryl group. The "alkyl group" in the reactive silicone includes, for example, a methyl group, an ethyl group, n- and i-propyl groups, n-, i- and t-butyl groups. Examples of the “cycloalkyl group” include a cyclohexyl group, and examples of the “aryl group” include a phenyl group. "Alkoxy group",
Examples of the “cycloalkoxy group” and “aryloxy group” include the same groups as described above in the description of compound (I).

When R ³ and R ⁶ are an alkoxy group, a cycloalkoxy group or an aryloxy group, these groups also function as “siloxane bond-forming groups”. The bond with I) or compound (II) may be stronger. Therefore, there is an advantage that bleeding of the unreacted reactive silicone from the cured product is reliably prevented. In particular, when R ³ and R ⁶ are a methoxy group, an ethoxy group, an n-propoxy group, or an i-propoxy group, the reactivity of these groups is favorable, so that it is preferable.

On the other hand, when R ³ and R ⁶ are an alkyl group, a cycloalkyl group or an aryl group, there is an advantage that such a reactive silicone is inexpensive and easily available.

Further, R ⁴ and R ⁵ are preferably a methyl group or an ethyl group, and more preferably all of R ⁴ and R ⁵ are a methyl group. This is because such a reactive silicone is inexpensive, easily available, and easily imparts so-called “silicone properties” such as releasability, surface lubricity and water / oil repellency. Also, the formula (I
R ⁷ is preferably an alkyl group for reasons of production of the compound shown in V). The alkyl group includes methyl, ethyl, n- or i-propyl, n-, i- or t.
-Butyl and the like are preferred.

In the above formulas (IV) and (V), n is 1 to
It is an integer of 10,000. If n exceeds 10,000, the viscosity of the reactive silicone is too high to make handling difficult, and the reactive silicone is less likely to be introduced into the condensate of the hydrolyzate of the compound (I) or the compound (II). . N is preferably an integer of 10 to 100. If it is in this range, it does not become extremely high viscosity,
Since it has practically sufficient reactivity and the silicone chain has a certain length or more, the properties of silicone in the cured product are favorably exhibited.

The siloxane bond forming group X ′ in the above formulas (IV) and (V) reacts with a hydroxysilyl group as it is or after hydrolysis to form “Si—O—Si”.
And a preferable example is a hydrogen atom, a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, or the like. Reactive silicones in which X 'is a halogen atom are not preferred because the reaction system is likely to be in an acidic atmosphere because hydrogen halide is generated by hydrolysis, and the oxetanyl group and the like may be opened.

The amount of the reactive silicone used is 1 to 100 parts by weight of the compound (I).
100 parts by weight is preferable, and 5 to 50 parts by weight is more preferable. If the amount of the reactive silicone is less than 1 part by weight, the properties of the silicone may not be sufficiently exhibited in the cured product. On the other hand, the amount of reactive silicone used is 1
If the amount is more than 00 parts by weight, the curability of the composition may decrease, the hardness of the cured product may decrease, or bleeding of unreacted reactive silicone may occur. (4) Hydrolysis Condensation Reaction The resin composition of the present invention comprises a compound (I) and a compound (II) or a condensate of a compound (I), a compound (II) and a hydrolyzate of a reactive silicone (hereinafter referred to as a condensate). , A hydrolyzate condensate).

The main reactions occurring here are the hydrolysis reaction of the compound (I) and the compound (II), and the hydrolysis reaction when the reactive siloxane has a siloxane bond forming group other than a hydroxyl group, and the two compounds ( A condensation reaction in which silicon atoms of I) or compound (II) are bonded via an oxygen atom,
And a condensation reaction in which the silicon atom of the compound (I) or the compound (II) and the silicon atom of the reactive silicone are bonded via an oxygen atom.

The above reaction is preferably performed in an atmosphere having a pH of 7 or more. The reason is that when the reaction is performed in an acidic atmosphere, the oxetanyl group or the like is easily opened, and the reactant is gelled by this, or the curability of the composition is reduced because the oxetanyl group or the like is consumed, or the like. It is. In order to maintain the atmosphere of the reaction solution at pH 7 or more, an alkali agent is usually added to the system. Examples of the alkaline agent include ammonia, inorganic bases such as alkali metal hydroxides, amine amounts,
It is preferable to use tetraalkylammonium hydroxide because tetraalkylammonium hydroxide and the like can be used, the activity as a basic catalyst is good, and the reaction can be easily controlled.

It is particularly preferable to carry out the above reaction in an atmosphere having a pH of 9 to 13. When the pH is less than 9, the production efficiency of the hydrolyzate condensate is reduced because the rates of hydrolysis and condensation of the compound (I), the compound (II) and the reactive silicone are low. On the other hand, when the pH exceeds 13, the amount of the alkali agent and the like used increases, so that it is not economical, and the step of removing the alkali agent and the like from the reaction system becomes complicated.

The other reaction conditions are not particularly limited, but the reaction temperature is preferably 10 to 120 ° C., more preferably 20 to 80 ° C., and the reaction time is preferably 2 to 80 ° C.
３０30 hours, more preferably 4-24 hours.

In this reaction, for example, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; and organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, hexane and ligroin are used. be able to. Among these, it is preferable to use a solvent that can uniformly dissolve the reaction system.

Further, the cationic photocurable resin composition comprises:
When a “reactive diluent having photocationic polymerizability” (hereinafter simply referred to as “reactive diluent”) is added, the viscosity of the composition is reduced or the physical properties of the cured product are adjusted. This is preferable because it is easy to carry out. (5) Reactive diluent One or two or more compounds selected from compounds having a photocationically polymerizable group such as a vinyloxy group, an epoxy group or an oxetanyl group can be used as the reactive diluent.

Specific examples of the reactive diluent include ethyl vinyl ether and the like having a vinyloxy group, bisphenol F diglycidyl ether and an aliphatic cyclic diepoxy resin having an epoxy group, and the like.
As a compound having an oxetanyl group, 1,4-bis [(3
1-ethyl-31-oxetanylmethoxy) methyl] benzene, 3-ethyl-31- (allyloxymethyl) oxetane, 3-ethyl-31- (hexyloxymethyl) oxetane, [31- (triethoxysilyl) -proproxymethyl Oxetane and the like.

Of these, it is preferable to use a compound having an epoxy group or an oxetanyl group, since a cured product having good heat resistance, excellent adhesive strength and good chemical resistance can be formed as described above.

By adjusting the viscosity of the resin composition using this reactive diluent, a composition excellent in workability such as coating properties can be obtained even though it is a solventless type. In addition, by changing the type and amount of reactive diluent,
The physical properties of the cured product can be adjusted to desired physical properties. In addition, the use of the reactive diluent can reduce the production cost of the resin composition.

The amount of the reactive diluent used in the composition of the present invention is preferably 5,000 parts by weight or less, more preferably 5 to 3,000 parts by weight, based on 100 parts by weight of the nonvolatile matter of the hydrolyzate condensate. More preferably
More preferably, it is 0 to 2000 parts by weight. If the amount of the reactive diluent exceeds 5000 parts by weight, the proportion of the perfluoroalkyl group and the silicone chain in the composition is reduced, and the cured product is less likely to exhibit properties such as water repellency and oil repellency. Become. (6) Other components The composition of the present invention can be cured by energy such as light or heat. When the curing means to be applied is light, it is preferable that a cationic photopolymerization initiator is added, When the curing means is heat, it is preferable that a heat cationic polymerization initiator is added. In this specification, light means ultraviolet light and visible light. It is preferable that the curing means is ultraviolet light because curing is quick and energy cost is low.

As the cationic photopolymerization initiator, those generally used can be used. For example, diallyliodonium salts and triarylsulfonium salts are preferably used. The addition amount of the photopolymerization initiator is preferably in the range of usually 0.1 to 10% by weight, and preferably 2 to 5% by weight based on the total weight of the non-volatile content of the hydrolyzate and the reactive diluent. % Is more preferable.

The cationic photocurable resin composition of the present invention may further contain general additives such as a viscosity modifier, a leveling agent, a stabilizer, and a silane coupling agent. In addition, the composition may contain an organic solvent, but its content is preferably at most 50% by weight, more preferably at most 20% by weight, based on the whole composition.

The specific effects of the above embodiment will be described below. According to the cationic photocurable resin composition of the embodiment,
The compatibility of each component is good, and the resulting cured product can exhibit good transparency while maintaining light transmittance.

According to the photocationically curable resin composition of the embodiment, since the composition is composed of, for example, a silsesquioxane compound into which a silicone chain is partially introduced, a silsesquioxane compound having no silicone chain Unlike the case where silicone and silicone are simply mixed, the cured product can be provided with silicone properties without causing compatibility problems.

According to the photocationic curable resin composition of the embodiment, the composition is composed of, for example, a compound having a silsesquioxane structure as a basic skeleton. A cured product having a higher surface hardness can be formed. Therefore, the resin composition is useful, for example, as a stain-resistant paint, a coating material for preventing graffiti, and further a protective coating material,
It can be used as a resin modifier, a resist material, an optical molding agent, and the like.

[0050]

The reason why the cured product of the resin composition of the present invention is excellent in stain resistance, water repellency and oil repellency and high in surface hardness is that the condensate of the hydrolyzate has a fluoroalkyl group It is presumed to have a sesquioxane structure. Further, since the condensate has an oxetanyl group, it is considered that the composition of the present invention can be rapidly cured even in the air.

When the condensate of the hydrolyzate is composed of the compound (I), the compound (II) and the reactive silicone, the cured product is peeled off because a silicone chain is partially introduced. , Surface lubricating properties and water / oil repellency, but the reason that the compatibility of the composition is good despite containing the silicone component is that the condensate forms It is presumed that it has been done.

Taking advantage of these characteristics, the resin composition of the present invention is useful, for example, as a stain-resistant paint and a coating material for preventing graffiti.

[0053]

EXAMPLES Hereinafter, the embodiment will be described more specifically with reference to examples. (Example 1) (1) Preparation of hydrolyzate condensate A hydrolyzate condensate was produced according to the following operations 1) to 4).

1) 200 ml equipped with stirrer and thermometer
In a reactor, a silicon compound represented by the following formula (VII) (hereinafter, referred to as
It is called “0xe-TRIES”. ) 45.67 g (14
2.5 mmol), a silicon compound represented by the following formula (VIII) (hereinafter, referred to as "C ₈ F ₁₇ -TRIES".) 4.58
g (7.5 mmol), N (CH ₃ ) ₄ OH as a catalyst
(10% aqueous solution) 4.55 g [H ₂ O 227.8 mmo
1, N (CH ₃ ) ₄ OH 5.0 mol], water 4.0 g (2
22.2 mmol) and 80.0 g of isopropyl alcohol (IPA) as a solvent were batchwise charged. Then, the reaction was allowed to proceed by stirring at room temperature.

[0055]

Embedded image

[0056]

Embedded image 2) The progress of the reaction was monitored by gel permeation chromatography (GPC). When 0xe-TRIES disappeared (about 20 hours), the reaction was terminated.

3) After completion of the reaction, 100 ml of toluene was added to the system, and the reaction solution was washed with saturated saline using a separating funnel. 4) Further, washing with water was repeated until the aqueous layer in the separating funnel became neutral, and then the organic layer was separated. Subsequently, anhydrous sodium sulfate was added to the organic layer for dehydration, and then toluene was distilled off under reduced pressure to obtain a desired photocationically curable hydrolyzate condensate.

The obtained hydrolyzate condensate has a number average molecular weight of about 2,000, and contains toluene, tetrahydrofuran (T
It was soluble in various general-purpose solvents such as HF), hexane and acetone, and was well compatible with the cationic photopolymerizable compound having an epoxy group or an oxetanyl group.

The above number average molecular weight is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). (2) Evaluation of cationic photocurable resin composition Next, a cationic polymerization initiator was added to the photocationically curable hydrolyzate condensate obtained as described above to prepare a coating agent. Using this coating material, the curability, the pencil hardness of the coating film surface, and the stain resistance were evaluated by the methods described below.

1) Curability A coating agent was applied on a glass substrate by using a bar coater for about 20 minutes.
It was applied to a thickness of μm, and was irradiated with ultraviolet rays under the following conditions, and the number of times of irradiation until the surface was tack-free was measured. (Ultraviolet irradiation conditions) Lamp: 80 W / cm high pressure mercury lamp, lamp height: 1
0 cm, Conveyor speed: 10 m / min, Irradiation atmosphere: in the air 2) Pencil hardness of coating film surface The coating agent was applied to a thickness of about 20 μm on a steel plate and a glass substrate using a bar coater, and the irradiation conditions described above were applied. UV irradiation was performed five times to obtain a cured film. This cured film is heated to temperature 2
After standing in a constant temperature room at 5 ° C and 60% humidity for 24 hours, J
The pencil hardness (scratch and peeling) of the coating film surface was measured according to IS K5400.

3) Stain resistance 24 gauze impregnated with aqueous red ink was applied to the surface of the coating film.
The test was carried out by allowing the test pieces to adhere for a period of time.

As a result, the tackiness of the coating agent disappeared by two irradiations of ultraviolet rays. An excellent hard coating film having a high hardness of about 5H in scratches and greater than 8H in peeling was obtained on the surface of the coating film which was irradiated with ultraviolet rays five times. Further, it was confirmed that there was no penetration of the red ink with respect to the stain resistance. Therefore, it was found that super water repellency, which is the property of fluorine derived from a perfluoroalkyl group, was favorably imparted to the coating film. (Example 2) In Example 1, the amount of 0xe-TRIES used was changed to 38.46 g (120.0 mmol) and C ₈
F ₁₇ -TRIES of use amount of 18.32g (30.0m
mol), and otherwise the same as in Example 1 to prepare a photocationically curable hydrolyzate condensate. The resulting hydrolyzate condensate was evaluated for curability, pencil hardness of the coating film surface, and stain resistance in the same manner as in Example 1.

As a result, the tackiness of the coating agent disappeared by two irradiations of ultraviolet rays. An excellent hard coating film having a high hardness of 4H and a peeling of 7H on the surface of the coating film subjected to the ultraviolet irradiation 5 times was able to be produced. Further, it was confirmed that there was no penetration of the red ink with respect to the stain resistance. (Example 3) 0xe-TRIES of Example 1 and the C ₈ F ₁₇
To the mixture with -TRIES, 8.0 g of a reactive silicone represented by the following formula (IX) was added, and reacted in the same manner as in Example 1 to obtain a photocationically curable hydrolyzate condensate. The reactive silicone used had a number average molecular weight of 2900.
And the degree of dispersion (weight average molecular weight / number average molecular weight) 1.38
belongs to.

[0064]

Embedded image Using the obtained hydrolyzate condensate, the curability, pencil hardness of the coating film surface, and stain resistance were evaluated in the same manner as in Example 1.

As a result, the tackiness of the coating agent disappeared by two irradiations of ultraviolet rays. An excellent hard coating film having a high pencil hardness of 5H and a peeling of 7H on the surface of the coating film subjected to the ultraviolet irradiation 5 times was able to be produced. Further, it was confirmed that there was no penetration of the red ink with respect to the stain resistance.

Further, a test for an oil-resistant ink was also conducted. That is, when a line was drawn with a black oil-based marker pen (using Hi-Mackey manufactured by Zebra) and the repelling condition of the ink was visually evaluated, it was confirmed that the ink was completely repelled. In addition, when a dry wiping test was performed 2000 times with a load of 500 g, it was confirmed that the ink was repelled after this test. In the composition of this example, since the silicone chain is chemically bonded to the hydrolyzate condensate having a silsesquioxane structure, the silicone chain is not removed from the surface of the cured film even by the dry wiping test. It is considered that good stain resistance was maintained. (Example 4) 0xe-TRIES of Example 1 and the C ₈ F ₁₇
To the mixture with -TRIES, 8.0 g of a reactive silicone represented by the following formula (X) was added and reacted in the same manner as in Example 1 to obtain a photocationically curable hydrolyzate condensate. The reactive silicone used had a number average molecular weight of 1000 having hydroxyl groups at both ends [trade name: X-21-5841 manufactured by Shin-Etsu Chemical Co., Ltd.].

[0067]

Embedded image Using the obtained hydrolyzate condensate, the curability, pencil hardness of the coating film surface, and stain resistance were evaluated in the same manner as in Example 1.

As a result, tackiness of the coating agent disappeared by two irradiations of ultraviolet rays. An excellent hard coating film having a high degree of pencil hardness of 5H and a peeling of 7H on the surface of the coating film subjected to the ultraviolet irradiation 5 times was able to be produced. Also, good results were obtained with respect to the stain resistance (red ink and oil-resistant ink) as in Example 3. (Example 5) As a reactive diluent having photocationic polymerizability with respect to 100 parts by weight of the photocationically curable hydrolyzate condensate obtained in Example 1, an aliphatic cyclic diepoxy resin [Daicel Chemical Industries, Ltd. ) Made by Celloxide 202
1] 500 parts by weight were added to prepare a photocationically curable resin composition. This photocationically curable resin composition was evaluated for curability, pencil hardness of the coating film surface, and stain resistance in the same manner as in Example 1.

As a result, the tackiness of the coating agent disappeared by two irradiations of ultraviolet rays. An excellent hard coating film having a high pencil hardness of 5H and a peeling of 7H on the surface of the coating film subjected to ultraviolet irradiation five times was able to be produced. In addition, good results were obtained for the stain resistance (red ink) as in Example 1. Example 6 An aliphatic cyclic diepoxy resin [Daicel Chemical Industries, Ltd.] was used as a reactive diluent having photocationic polymerizability with respect to 100 parts by weight of the photocationically curable hydrolyzate condensate obtained in Example 4. Celoxide 20
21] was added to prepare a photocationically curable resin composition. This composition was evaluated for curability, pencil hardness of the coating film surface, and stain resistance in the same manner as in Example 4.

As a result, the tackiness of the coating agent disappeared by two irradiations of ultraviolet rays. An excellent hard coating film having a high pencil hardness of 5H and a peeling of 7H on the surface of the coating film subjected to the ultraviolet irradiation 5 times was able to be produced. Also, good results were obtained with respect to the stain resistance (red ink and oil-resistant ink) as in Example 4.

The technical ideas grasped from the above embodiment will be described below. (A) The cationic photocurable resin composition according to claim 1 or 2, wherein R ¹ in the formula (II) is an organic functional group represented by the following structural formula (III).

[0072]

Embedded image (However, m is a positive number of 0 to 10, and R ² has 1 to 1 carbon atoms.
4 alkylene group. With this configuration, the compound as a fluoroalkyl group such as water / oil repellency and stain resistance can be effectively exhibited, and the compound represented by the formula (II) can be easily produced and easily obtained. .

(B) The cationic photocurable composition according to claim 2, wherein the reactive silicone is at least one selected from compounds represented by the following formulas (IV) and (V). Resin composition.

[0074]

Embedded image (Where X 'is a siloxane bond-forming group, R ³ and R ⁶ are each an alkoxy group, cycloalkoxy group, aryloxy group, alkyl group, cycloalkyl group or aryl group, and R ⁴ , R ⁵ and R ⁷ are Each is an alkyl group, a cycloalkyl group or an aryl group, and n is 1 to 1000
It is a positive number of 0. )

[0075]

Embedded image (Where X 'is a siloxane bond-forming group, R ³ and R ⁶ are each an alkoxy group, cycloalkoxy group, aryloxy group, alkyl group, cycloalkyl group or aryl group, R ⁴ and R ⁵ are alkyl groups, A cycloalkyl group or an aryl group, and n is a positive number of 1 to 10000.) In such a configuration, water repellency and water repellency are based on the reactive silicone represented by the formula (IV) or (V). Oiliness can be improved and the degree of crosslinking can be adjusted.

(C) The cationic photocurable resin composition according to (b), wherein n in the formula (IV) or (V) is a positive number of 10 to 100. With this configuration,
Compatibility of the composition of the formula (IV) or the formula (V) is increased, and transparency can be improved.

(D) In the above formula (I) or (II), each of X is an alkoxy group, a cycloalkoxy group or an aryloxy group, and R ⁰ is an organic functional group having an oxetanyl group. Item 1, Item 2, and the cationic photocurable resin composition according to any one of the above (a), (b) and (c).

With this configuration, the curability of the cationic photocurable resin composition can be improved. (E) R ⁰ in the formula (I) is an organic functional group represented by the structural formula shown in the following formula (VI), wherein the above (a), (b), and (c) And the cationic photocurable resin composition according to any one of (d).

[0079]

Embedded image (However, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁹ is an alkylene group having 2 to 6 carbon atoms.) In this case, a cured product obtained from the resin composition Can be improved, and the formula (I)
Are simple and easily available.

The cationic photocurable resin composition according to claim 1 or 2, further comprising (f) a condensate of the hydrolyzate and a reactive diluent having cationic photopolymerizability. When configured in this way, in addition to the effects of the invention described in claim 1 or 2, the viscosity is adjusted based on the reactive diluent having photocationic polymerizability, and the coatability is improved without using a solvent. And the like, and the physical properties of the cured product can be adjusted by the type and amount of the reactive diluent used.

[0081]

As described above, according to the present invention, the following effects can be obtained. According to the photocationic curable resin composition of the first invention, the hydrolyzate condensate of compound (I) and compound (II) contains an organic functional group such as a fluoroalkyl group and an oxetanyl group. ing. Therefore, based on these organic functional groups, it is possible to obtain a cured product such as a coating film having excellent water repellency, oil repellency and stain resistance and high hardness.

According to the photo-cationic curable resin composition of the second invention, in addition to the effects of the first invention, a coating film is formed based on a reactive silicone having one or more siloxane bond-forming groups in one molecule. Can more effectively impart the properties of silicone.

Continuation of the front page (72) Inventor Akira Sumi 1-1-1, Funami-cho, Minato-ku, Nagoya-shi, Aichi F-term in Nagoya Research Institute, Inc. (reference) 4J002 CP171 CP191 GH01 4J038 DL031 DL032 DL051 DL052 DL071 DL072 GA02 GA07 KA03 KA06 NA05 NA17 PA17 PB09

Claims (2)

[Claims] 1. A compound comprising a condensate of a hydrolyzate of a compound represented by the following structural formula (I) and a compound represented by the following structural formula (II): Photo-curable resin composition. Embedded image (However, R ⁰ is an organic functional group having an epoxy group or an oxetanyl group, and X is a hydrolyzable group.) (However, R ¹ is an organic functional group having a fluoroalkyl group, and X is a hydrolyzable group.) 2. The cationic photocurable resin composition according to claim 1, wherein the condensate of the hydrolyzate also has a reactive silicone having one or more siloxane bond-forming groups in one molecule as a constituent. .