JPH11199673A - Photo-cationically hardenable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having an improved compatibility with a silicone, further having silicone characteristics and capable of forming a hardened product with a high hardness by hydrolyzing a compound having an oxetane group or the like with a reactive silicone. SOLUTION: This composition comprises a hydrolyzate obtained by hydrolyzing a mixture of (A) a compound of formula I (R<0> is an organic functional group having epoxy or oxetanyl, preferably oxetanyl; X is a hydrolyzable group) with (B) a reactive silicone having one or more siloxane bond-forming groups in one molecule, preferably a compound of formula II (X' is a siloxane bond- forming group; R<1> and R<4> are each an alkoxy, a cycloalkoxy or the like; R<2> and R<3> are each an alkyl, an aryl or the like; (n) is a positive number of 1-10000) or the like. The composition of the mixture to be hydrolyzed comprises preferably 1-100 pts.wt. component B based on 100 pts.wt. component A. The composition is, for example, useful as a stain-resistant paint or a coating material for preventing graffiti.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cationically photocurable resin composition, and more particularly, to a resinous composition containing a silsesquioxane compound having a cationically photopolymerizable functional group and having a silicone chain introduced. . Since the cured product formed from the photocationically curable resin composition of the present invention has the properties of silicone, it is useful as, for example, a stain-resistant paint and a coating material for preventing graffiti.

[0002]

2. Description of the Related Art In the field of ultraviolet (UV) -initiated polymerization or ultraviolet-initiated curing, photoinitiated radical polymerization using polyfunctional acrylates and unsaturated polyesters has been widely studied and industrially used.

However, there is a problem that this radical polymerization is inhibited by oxygen in the air or the like. Especially when the coating composition is cured by radical polymerization,
As the film thickness of the composition becomes thinner, the influence of polymerization inhibition by oxygen becomes remarkable, and there is a limitation that the composition must be cured under an inert atmosphere in order to cure the composition quickly and completely.

[0004] On the other hand, the photoinitiated cationic polymerization is not affected by polymerization inhibition by oxygen unlike the photoinitiated radical polymerization, and can be completely polymerized even in the air. In particular, according to the composition using a silicone-based epoxide or oxetane compound as a monomer, it is possible to obtain a cured product having good heat resistance and chemical resistance, excellent adhesive strength, and good stain resistance. JP-A-6-16804 discloses compounds of the above-mentioned monomers in which oxetanyl groups are introduced into both ends of silicone. The present applicant has previously filed a patent application relating to a method for producing a compound having an oxetanyl group introduced into both ends of the silicone (Japanese Patent Application No. 9-14098).
No. 4).

[0005]

However, a cured product formed from a photocationically curable composition using the above-mentioned silicone-based epoxide or oxetane compound as a monomer,
In general, since the basic skeleton structure is made of silicone or polyether, there is a problem that the surface hardness tends to be insufficient when used as a coating agent, for example.

On the other hand, the present applicant has previously filed a patent application for a photocationically curable hard coat agent composition including a photocationically curable composition comprising a silsesquioxane compound having an oxetanyl group (Japanese Patent Application No. 2002-282,197). Hei 9-19773
No. 7). However, a cured film of this composition usually does not exhibit so-called "silicone properties" such as stain resistance and water / oil repellency. Therefore, as a means for imparting silicone properties to the cured film of the hard coat agent composition, it is conceivable to mix a silicone compound with this composition.

However, since the above cationic photocurable composition has poor compatibility with silicone, if a silicone compound is simply used as a mixture with the composition, the composition may become non-uniform, In the above, problems such as repelling or bleeding of the silicone compound from the cured product were likely to occur.

An object of the present invention is to provide a photocationically curable resin composition capable of forming a cured product having high hardness and silicone characteristics.

[0009]

Means for Solving the Problems The inventors of the present invention have achieved high hardness without using the above-mentioned compatibility problem by using a photocationically polymerizable silsesquioxane compound into which a silicone chain has been introduced in advance. The present invention has been completed by finding that a cured product having the characteristics of silicone can be formed.

That is, the cationic photocurable resin composition of the first invention in the present invention comprises a compound represented by the following structural formula (I) and one or more siloxane bond-forming groups in one molecule. And a hydrolyzate obtained by hydrolyzing a mixture of the reactive silicone and the reactive silicone.

[0011]

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Here, the “siloxane bond forming group” refers to the silicon atom of the compound represented by the structural formula (I) in the hydrolysis (hereinafter referred to as “compound (I)”). A group capable of forming a siloxane bond between
Examples include a hydrogen atom, a hydroxyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a halogen atom and the like.

The hydrolyzate in the first invention comprises a compound obtained by co-condensing the compound (I) with the reactive silicone, that is, a silsesquioxane compound into which a silicone chain is partially introduced. The silicone chain imparts silicone properties to the cured product and the compound
Unlike the case where a silicone compound is mixed with a silsesquioxane compound obtained by hydrolyzing (I) alone, compatibility is a problem because the silicone chain is chemically bonded to the silsesquioxane compound. It will not be.

The cationic photocurable resin composition comprises a second
As in the invention, a reactive diluent having photocationic polymerizability can be contained. By adjusting the viscosity with this reactive diluent, it is possible to obtain a composition that is excellent in operability such as coating properties while being solventless. Further, the physical properties of the cured product can be adjusted by the type and amount of the reactive diluent.

The reactive silicone in the composition of the first invention or the second invention has the following formula (I) as in the third invention.
It is preferably at least one selected from compounds represented by the structural formula represented by I) or the following formula (III).

[0016]

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[0017]

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In the above formulas (II) and (III), n
Is preferably a positive number of 10 to 100 as in the fourth invention.

Further, the compositions of the first to fourth inventions include:
As in the fifth invention, it is preferable that all of X in the above formula (I) are an alkoxy group, a cycloalkoxy group or an aryloxy group, and that R ⁰ is an organic functional group having an oxetanyl group.

Further, the composition of the first to fifth inventions is characterized in that, as in the sixth invention, R ⁰ in the above formula (I) is an organic functional group represented by the following structural formula (IV). Preferably, there is.

[0021]

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[0022]

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

(1) Compound (I) R ⁰ in the above formula (I) is an organic functional group partially having at least one epoxy group or oxetanyl group. In the present invention, R ⁰ is preferably an organic functional group having an oxetanyl group. This is because the photopolymerization rate of oxetanyl groups is usually significantly faster than epoxy groups. In particular, the compound (I) in which R ⁰ has an oxetanyl group is suitably used for applications requiring rapid photocurability, such as when coating on paper or plastic. Moreover, the oxetane-type monomer tends to have a higher degree of polymerization during photocuring than the epoxide-type monomer, so that various physical properties tend to be better.

In the present invention, R ⁰ is particularly preferably an organic functional group represented by the structural formula shown in the above formula (IV). In the formula (IV), R ⁶ is a hydrogen atom or a group having 1 to 1 carbon atoms.
It is particularly preferred that R ⁶ is an alkyl group and R ⁶ is an ethyl group. R ⁷ is an alkylene group having 2 to 6 carbon atoms, and R ⁷ is particularly preferably a propylene group. This is because it is easy to obtain or synthesize such an oxetane compound that forms an organic functional group. Further, it is not preferable that the carbon number of R ⁶ or R ⁷ in the formula (I) is 7 or more, because the surface hardness of the cured product tends to be insufficient.

The hydrolyzable group X in the above formula (I) is
The group is not particularly limited as long as it is a group having hydrolyzability, and may be a halogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group, or the like. Further, one molecule of this compound contains three X's, and these may be all the same group or two or more different groups. In the present invention, it is preferably an alkoxy group, a cycloalkoxy group or an aryloxy group as in the fifth invention. This is because, 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, so that an epoxy group or an oxetanyl group (hereinafter also referred to as “oxetanyl group or the like”) is opened. This is because there is a risk of ringing.

The above "alkoxy group" includes, for example, methoxy group, ethoxy group, n- and i-propoxy group,
and n-, i- and t-butoxy groups. 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. Of these, X has 1 to 1 carbon atoms because the alkoxy group has good hydrolyzability.
It is preferably an alkoxy group of 3. X is particularly preferably an ethoxy group because the raw materials are easily available and the hydrolysis reaction is easy to control.

(2) Reactive Silicone The reactive silicone in the present invention can be used without particular limitation as long as it is a compound having one or more "siloxane bond forming groups" in one molecule. .
The reactive silicone is preferably a linear or branched linear silicone, and may have the above-described siloxane bond-forming group at the side chain or at the terminal.

In the composition of the present invention, as in the third invention, the above-mentioned formulas (II) and (III) are used as reactive silicones.
It is preferable to use at least one selected from the compounds represented by the structural formulas shown below. Where R ¹ and R ⁴
Is a substituent selected from an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group and an aryl group. The above formula (II) and
Two R ¹ contained in one molecule of the compound shown in (III) may be the same group or different groups. This also applies to R ^4.

R ² and R ³ are an alkyl group, a cycloalkyl group or an aryl group, respectively. R ² and R ³ may be the same group or different groups. Further, may be an n-number of R ² is also different for two or more be all the same radical groups contained in one molecule, R ³
The same applies to. R ⁵ 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. Examples of the “alkoxy group”, “cycloalkoxy group” and “aryloxy group” include the same groups as described above in the description of compound (I).

Wherein R ¹ and R ⁴ are an alkoxy group,
When it is a cycloalkoxy group or an aryloxy group,
Since these groups also function as “siloxane bond forming groups”, the bond between the reactive silicone and silsesquioxane can be stronger. Therefore,
There is an advantage that bleeding of unreacted reactive silicone in the cured product is reliably prevented. In particular, when R ¹ and R ⁴ are a methoxy group, an ethoxy group, an n-propoxy group or an i-propoxy group, these groups are preferred because of good hydrolyzability. On the other hand, R ¹ and R ⁴
Is 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 ² and R ³ are preferably a methyl group or an ethyl group, and more preferably all of R ² and R ³ are a methyl group. Such reactive silicones are inexpensive and readily available,
This is because so-called “characteristics of silicone” such as releasability, surface lubricity, and water / oil repellency are easily imparted. In addition, R ⁵ is preferably an alkyl group for the production of the compound represented by the formula (III). The alkyl group includes methyl, ethyl, n- or i-propyl, n-, i
-Or t-butyl is preferred.

In the above formulas (II) and (III), n is 1 to
It is a positive number of 10,000. When n exceeds 10,000, the viscosity of the reactive silicone is too high to make handling difficult, and the reactive silicone becomes difficult to be introduced into silsesquioxane. This n is 1 as in the fourth invention.
It is preferably a positive number from 0 to 100. Within this range, the viscosity does not become extremely high, the reactivity is practically sufficient, and the silicone chain has a length of a certain degree or more, so that the properties of the silicone can be sufficiently exhibited in the cured product.

The siloxane bond forming group X 'in the above formulas (II) and (III) is preferably a hydrogen atom, a hydroxyl group, an alkoxy group, a cycloalkoxy group or an aryloxy group. 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 thus the oxetanyl group and the like may be opened.

The composition of the “mixture” subjected to hydrolysis is:
It is preferable to use 1 to 100 parts by weight (more preferably 5 to 50 parts by weight) of the reactive silicone per 100 parts by weight of the compound (I). 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, if the amount of the reactive silicone exceeds 100 parts by weight, the curability of the composition may decrease, the hardness of the cured product may decrease, or bleeding of the unreacted reactive silicone may occur.

(3) Hydrolysis Reaction The composition of the present invention comprises a hydrolyzate obtained by hydrolyzing a mixture of the compound (I) and the reactive silicone (hereinafter simply referred to as “hydrolyzate”). Become. Here, the hydrolysis is preferably performed in an atmosphere having a pH of 7 or more.
This is because oxetanyl groups and the like are liable to open when hydrolyzed in an acidic atmosphere, which causes gelation of the system or reduces the curability of the composition because the oxetanyl groups and the like are consumed. is there. In order to make the atmosphere during the hydrolysis at pH 7 or more, an alkali agent is usually added to the system. As the alkaline agent, ammonia,
Quaternary ammonium salts, organic amines, and the like can be used, and quaternary ammonium salts are preferably used because they have good activity as a basic catalyst. Further, it is particularly preferable that the hydrolysis is performed in an atmosphere having a pH of 9 to 13. p
When H is less than 9, the hydrolysis / condensation rate of the compound (I) and the reactive silicone is low, so that the production efficiency of the hydrolyzate is reduced. 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 at the time of hydrolysis are not particularly limited.
120 ° C (more preferably 20 to 80 ° C), and a suitable reaction time is 2 to 30 hours (more preferably 4 to 24 hours). The organic solvent used in the hydrolysis is not particularly limited, and examples thereof include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, toluene, 1,4-dioxane, hexane, and the like.
Ligroin or the like can be used. Among them, those capable of uniformly dissolving the reaction system are preferable.

(4) Reactive Diluent The cationic photocurable resin composition of the present invention is used for reducing the viscosity of the composition or adjusting the physical properties of the cured product.
It may contain a "reactive diluent having photocationic polymerizability" (hereinafter, simply referred to as "reactive diluent"). As the reactive diluent, one or two or more compounds selected from compounds having a cationic photopolymerizable group such as a vinyloxy group, an epoxy group or an oxetanyl group can be used.

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

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

The amount of the reactive diluent used in the composition of the present invention is preferably 200 parts by weight or less based on 100 parts by weight of the non-volatile matter of the hydrolyzate, and is preferably 5 to 1 part.
It is more preferably 50 parts by weight, further preferably 10 to 100 parts by weight. If the amount of the reactive diluent exceeds 200 parts by weight, the proportion of the silicone chain in the composition will be small, and it will be difficult for the cured product to exhibit the properties of silicone.

(5) Other Components The cationic photocurable resin composition of the present invention may contain various commonly used cationic photopolymerization initiators. For example, diallyliodonium salts and triarylsulfonium salts are preferably used. The amount of the photopolymerization initiator to be added is generally preferably in the range of 1 to 10% by weight, preferably 3 to 5% by weight, based on the total weight of the nonvolatile matter of the hydrolyzate and the reactive diluent. Is more preferable.

Further, 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. The composition may contain an organic solvent, but the content is preferably 50% by weight or less, more preferably 20% by weight or less based on the whole composition.

The composition of the present invention comprises a silsesquioxane compound partially having a silicone chain introduced therein.
The properties of silicone can be imparted to the cured product, and a cured product having a high surface hardness can be formed because the basic skeleton of the compound has a silsesquioxane structure. Further, since it is an oxetane-type photocurable resin composition, it can be polymerized quickly and completely even in the air.
Taking advantage of these features, the composition of the present invention is useful, for example, as a stain-resistant paint, a coating material for preventing graffiti, and further, can be used as a protective coating material, a resin modifier, a resist material, an optical molding agent, and the like. is there.

[0045]

The present invention will be described more specifically with reference to the following examples. Incidentally, the number average molecular weight in the present specification,
It is the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

(1) Synthesis of Silicone Chain-Introduced Silsesquioxane Compound (Synthesis Example 1) A silicon compound represented by the following formula (V)
It is called “Oxe-TRIES”. ) And a reactive silicone represented by the following formula (VI) (hereinafter referred to as “OH-Silicone”) was hydrolyzed to obtain a cationic photopolymerizable resin composition. The OH-Silicone used was "DMS-S21" (trade name, a number average molecular weight of about 4,200) manufactured by Chisso Corporation.

[0047]

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[0048]

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Hereinafter, the reaction operation will be described. (1) 30 g of isopropyl alcohol and 2.73 g of a 10% aqueous solution of tetramethylammonium hydroxide (hereinafter also referred to as “Me ₄ NOH”) were placed in a reactor equipped with a stirrer and a thermometer (H ₂ O; 136.5 mmol, Me ₄ NO
H; 3.0 mmol), water 0.78 g (43.3 mmol)
After charging l), 19.23 g of Oxe-TRIES
(60.0 mmol) and 1.5 g of OH-Silicone (0.
(36 mmol) was slowly added and left stirring at room temperature. The progress of the reaction was monitored by gel permeation chromatography, and the reaction was terminated when Oxe-TRIES almost disappeared (about 20 hours after the start of the addition of the mixture). At this time, the pH of the reaction system was 11.5. (2) After the 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. (3) After repeatedly washing with water until the aqueous layer of the separating funnel becomes neutral, the organic layer is separated, dehydrated with anhydrous sodium sulfate, and toluene is distilled off under reduced pressure to obtain the desired silicone. A chain-introduced silsesquioxane compound A (that is, a “hydrolysate” described in the claims) was obtained. This compound A is in the form of a white turbid liquid, and has a number average molecular weight of about 2,
000.

The obtained silicone-chain-introduced silsesquioxane compound A is soluble in general-purpose solvents such as toluene, tetrahydrofuran, hexane and acetone, and a small amount of these solvents (for example, when the solids concentration of compound A is 70% by weight). %
By adding the following amounts), it became colorless and transparent. On the other hand, a silsesquioxane compound obtained by hydrolyzing only Oxe-TRIES (that is, not co-condensed with OH-Silicone) is separately synthesized (hereinafter, this compound is referred to as “silsesquioxane compound a”). When this silsesquioxane compound a was mixed with OH-Silicone, they were not compatible at all, and the solid content concentration was 50% by weight.
Was not compatible at all as an organic solvent solution. This result suggests that the silsesquioxane compound in Compound A has a silicone chain bonded thereto.

It should be noted that the compound A obtained in Synthesis Example 1 was in the form of a fine white turbid state when it did not contain an organic solvent.
This hydrolyzate is a mixture of silsesquioxane having various structures into which silicone chains have been introduced and silsesquioxane having various structures into which silicone chains have not been introduced. It is presumed that there is something. On the other hand, when OH-Silicone having a smaller number average molecular weight than that of Synthesis Example 1 is used, a hydrolyzate having higher compatibility between compounds contained in the hydrolyzate can be obtained. For example, a number average molecular weight of about 2,000
The hydrolyzate obtained by using OH-Silicone 0 in the same manner as in Synthesis Example 1 in other respects was colorless and transparent even when no organic solvent was contained.

(Synthesis Example 2) Oxe-TRIES and a reactive silicone represented by the following formula (VII) (hereinafter referred to as “H-Silic”)
one. ) Was hydrolyzed to obtain a cationic photopolymerizable resin composition. As the H-Silicone, one having a number average molecular weight of about 2,900 and a dispersity of 1.38 was synthesized and used.

[0053]

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Hereinafter, the reaction operation will be described. (1) 60 g of isopropyl alcohol and a 10% aqueous solution of Me ₄ NOH were placed in a reactor equipped with a stirrer and a thermometer.
_{46g (H 2 O; 273.0mmol,} Me 4 NOH;
6.0 mmol) and 1.56 g (87 mmol) of water, and then 38.46 g of Oxe-TRIES (120.
0 mmol) and 3.0 g (1.03 mmol) of H-Silicone
l) was gradually added, and the mixture was left to stir at room temperature. The progress of the reaction was monitored by gel permeation chromatography, and the reaction was terminated when Oxe-TRIES almost disappeared (about 20 hours after the start of the addition of the mixture). At this time, the pH of the reaction system was 11.5. (2) After completion of the reaction, the same treatment as in Synthesis Example 1 was performed to obtain a silicone chain-introduced silsesquioxane compound B. This compound B is a white turbid substance and has a number average molecular weight of about 2,000.
Met. Further, similarly to Compound A obtained in Synthesis Example 1, the compound was soluble in general-purpose solvents such as toluene, tetrahydrofuran, hexane, and acetone.

(2) Preparation of Photocationic Curable Resin Composition (Examples 1 and 2) Silicone chain-introduced silsesquioxane compounds A and B obtained in Synthesis Examples 1 and 2, each 100
3 parts by weight of bis (dodecylphenyl) iodonium hexafluoroantimonate as a cationic photopolymerization initiator and 10 parts by weight of toluene for decreasing the viscosity were added to the parts by weight, and A cationically curable resin composition was prepared.

(Examples 3 to 13) The silicone chain-introduced silsesquioxane compounds A and B obtained in Synthesis Examples 1 and 2 were mixed with a reactive diluent at the ratios shown in Table 1 below, and further mixed with a cation. Example 3 was mixed with bis (dodecylphenyl) iodonium hexafluoroantimonate (3% by weight based on the total weight of the silicone chain-introduced silsesquioxane compound and the reactive diluent) as the reactive photopolymerization initiator. To 13 photo-cationic curable resin compositions were prepared. In Table 1, “Oxe-TRIES” is [3-
(Triethoxysilyl) -proproxymethyl] oxetane, “Hexyl-Oxe” is 3-ethyl-3- (hexyloxymethyl) oxetane, “Allyl-Oxe” is 3-ethyl-
3- (allyloxymethyl) oxetane, “Epoxy” indicates γ-glycidoxypropyltriethoxysilane.
Further, the compositions of Examples 1 to 13 are all transparent,
It showed that the compatibility of each component was good.

(Comparative Example 1) With respect to 100 parts by weight of a silsesquioxane compound a into which a silicone chain was not introduced,
Bis (dodecylphenyl) iodonium hexafluoroantimonate as a cationic photopolymerization initiator was added in an amount of 3 parts by weight, and 10 parts by weight of toluene was further added to prepare a cationically photocurable resin composition of Comparative Example 1.

[0058]

[Table 1]

(3) Evaluation of cationic photocurable resin compositions The photocurable curable resin compositions of Examples 1 to 13 and Comparative Example 1 were evaluated for curability, pencil hardness and stain resistance by the following methods. . The results are shown in Table 2 below.

(1) Curability Each composition was coated on a glass substrate for about 2 hours using a bar coater.
It was applied to a thickness of 0 μm and irradiated with ultraviolet rays under the following conditions, and the number of times of irradiation until the tack on the surface disappeared was measured. [UV irradiation conditions] Lamp: 80 W / cm high-pressure mercury lamp Lamp height: 10 cm Conveyor speed: 10 m / min Irradiation atmosphere: in air

(2) Pencil Hardness Each composition was applied to a thickness of about 20 μm on a steel plate and a glass substrate using a bar coater, and was applied under the irradiation conditions described above.
Irradiation was performed twice to obtain a cured film. After leaving this cured film in a constant temperature room at a temperature of 25 ° C. and a humidity of 60% for 24 hours, the pencil hardness of the surface was measured according to JIS K5400.

(3) Stain resistance A line is drawn on the surface of the cured film (after leaving for 24 hours) obtained in the above (2) with a black oily marker (using Zebra Hi-Mackie) to repel ink. The condition was visually evaluated. The evaluation results were as follows: 〇: Completely repelled (stain resistance was good), △: Slight ink remained (stain resistance was almost good),
X: Not repelled (poor stain resistance), expressed in three stages.

[0063]

[Table 2]

As shown in Table 2, Comparative Example 1 comprising a silsesquioxane compound into which no silicone chain was introduced.
Although the cured film formed from the composition (1) has excellent surface hardness, it does not have the properties of silicone and thus has poor stain resistance. On the other hand, Examples 1 to 13 comprising a silsesquioxane compound into which a silicone chain was introduced according to the present invention were used.
Each of the cured films formed from the above compositions shows good or almost good stain resistance, and it is understood that these cured films have silicone properties. The cured films formed from the compositions of Examples 1 to 13 were all excellent in surface hardness.

The cured films of Examples 1 to 13
When a wiping test was performed from 1000 times of gauze with a load of 00 g, it was confirmed that the ink was repelled even after this test. Since the silicone chain is bonded to the silsesquioxane compound in the composition of the present invention, the silicone chain is not removed from the surface of the cured film by the wiping test from the above, and good stain resistance is maintained. It is thought that it was.

In a neutral atmosphere, γ-glycidoxypropyltriethoxysilane (that is, R ⁰ in the formula (I) is an organic functional group having an epoxy group) is used in place of Oxe-TRIES. The performances of the composition and the cured film of the various hydrolyzates obtained by the hydrolysis tended to be almost the same.

The present invention is not limited to the specific embodiments described above, but may be variously modified within the scope of the present invention in accordance with the purpose and application.

[0068]

The photocationically curable resin composition of the present invention is composed of a silsesquioxane compound partially having a silicone chain introduced therein. Therefore, the silsesquioxane compound having no silicone chain is combined with silicone. Unlike the case of simply mixing, it is possible to impart the properties of silicone to the cured product without causing compatibility problems. Further, since the composition of the present invention is composed of a compound having a silsesquioxane structure as a basic skeleton, it is possible to form a cured product having a higher surface hardness as compared with a compound whose basic skeleton is made of silicone, polyether or the like. Therefore, the composition of the present invention is useful, for example, as a stain-resistant paint, a coating material for preventing graffiti.

Claims (6)

[Claims] 1. A compound obtained by hydrolyzing a mixture of a compound represented by the following structural formula (I) and a reactive silicone having one or more siloxane bond-forming groups in one molecule. A cationic photocurable resin composition comprising a decomposition product. Embedded image 2. The cationic photocurable resin composition according to claim 1, comprising the hydrolyzate and a reactive diluent having cationic photopolymerizability. 3. The cationic photocurable composition according to claim 1, wherein the reactive silicone is at least one selected from compounds represented by the structural formulas represented by the following formulas (II) and (III). Resin composition. Embedded image Embedded image 4. The cationic photocurable resin composition according to claim 3, wherein n in the formulas (II) and (III) is a positive number of 10 to 100. 5. The compound according to claim 1, wherein in the formula (I), 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. The photocationically curable resin composition according to any one of the preceding claims. 6. In the above formula (I), R ⁰ is the following formula (I)
The cationic photocurable resin composition according to any one of claims 1 to 5, which is an organic functional group represented by a structural formula shown in V). Embedded image