JP2000234024A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can form a cured product being excellent in water repellency, oil repellency, and staining resistance and having a high hardness by selecting a composition comprising a condensate of the cohydrolyzate of two compounds each having a specified structure. SOLUTION: This composition comprises a condensate of the cohydrolyzate of 20-95 wt.% compound represented by formula I and 80-5 wt.% compound represented by formula II or of a mixture formed by mixing the above compounds with a reactive silicone having at least one siloxane bond forming group in the molecule and represented by formula III or the like. The composition may additionally contain at most 5,000 pts.wt., per 100 pts.wt. condensate, a viscosity modifier, a stabilizer, a photic or thermal polymerization initiator, etc. The above hydrolysis and the above condensation are performed in the presence of an alkali agent such as ammonia in an atmosphere at a pH of 9-13. In the formulae, R0 is an organic functional group having (meth)acryloyl; X is a hydrolyzable group; X' is a siloxane forming group; R3 and R6 are each an alkoxyl, an aryl or the like; R4 and R5 are each an alkyl or the like; R7 is a cycloalkyl or the like; and (n)is 1-10,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition which can be cured by, for example, ultraviolet rays to form a coating film. More specifically, the present invention relates to a novel curable resin composition having a radically polymerizable functional group and having a fluoroalkyl group.
The composition can be cured by energy such as ultraviolet light, electron beam, X-ray or heat, and the obtained cured product has a fluoroalkyl group.
It is useful as a coating material for preventing graffiti.

[0002]

2. Description of the Related Art In general, as a curable compound having radical polymerizability, polyfunctional acrylates and unsaturated polyesters have been widely studied and are used industrially.

In addition, various studies have been made for the purpose of imparting properties such as stain resistance and peelability to a cured product obtained by using a radical polymerizable curable compound. In addition, the releasability of the cured product means the ease of removing a layer such as a coating film, a pressure-sensitive adhesive layer, and an adhesive layer formed on the surface of the cured product.

[0004] However, a composition obtained by mixing a silicone compound such as an organopolysiloxane with a radically polymerizable curable compound, which has been frequently used, is difficult to obtain because of poor compatibility. It has problems such as release of the silicone compound from the cured product.

In order to solve these problems, the present inventors have previously described an acryloyl group or a methacryloyl group [hereinafter collectively referred to as a (meth) acryloyl group] at the end of a silicone compound. (JP-A-10-158404). The curable resin composition comprising the resin obtained by this production method becomes more uniform, and the cured product is one in which the silicone compound is hardly released.

[0006]

However, the cured product obtained from the curable resin composition described in JP-A-10-158404 has not yet had sufficient hardness for some purposes. In addition, there is a problem that long-time stain resistance is poor depending on the use environment.

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 radically curable resin composition which is excellent in water / oil repellency and stain resistance and can form a cured product having high hardness.

[0008]

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 curable resin composition of the first invention comprises both a compound represented by the following structural formula (I) and a compound represented by the following structural formula (II): It comprises a condensate of a hydrolyzate.

[0010]

Embedded image (However, R ⁰ is an organic functional group having a (meth) acryloyl group, and X is a hydrolyzable group.)

[0011]

Embedded image (However, R ¹ is a fluoroalkyl group, and X is a hydrolyzable group.) In the curable resin composition of the second invention, the condensate of the hydrolyzate in the first invention The present invention is characterized in that a reactive silicone having one or more siloxane bond-forming groups in one molecule is also included as a component.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The curable resin composition of the present invention comprises a compound represented by the following structural formula (I) (hereinafter, referred to as compound (I)) and a compound represented by the following structural formula (II) (Hereinafter, referred to as compound (II)) which is a condensate of a hydrolyzate obtained by a hydrolysis reaction.

[0013]

Embedded image (However, R ⁰ is an organic functional group having a (meth) acryloyl group, and X is a hydrolyzable group.)

[0014]

Embedded image (However, R ¹ is a fluoroalkyl group and X is a hydrolyzable group.) First, the compound (I) and the compound (II) will be described in detail. (1) Compound (I) As the organic functional group R ⁰ having a (meth) acryloyl group contained in the compound (I), a compound having a monovalent organic functional group represented by the following formula (VI) is a compound It is preferable because it is easy to obtain or produce (I).

[0015]

Embedded image (In the above formula (VI), R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is an alkylene group having 1 to 6 carbon atoms.) Among these organic functional groups, the alkylene group is particularly a propylene group. Those are preferred because the compound (I) is easily available or manufactured.

The compound (I) can be obtained, for example, by an addition reaction of allyl acrylate or allyl methacrylate with a silicon compound having a Si—H bond and a hydrolyzable group. This reaction is carried out in the presence of a catalyst, such as cobalt, nickel, ruthenium, rhodium,
A simple substance of a Group 8 to Group 10 metal such as palladium, iridium, and platinum, an organic metal complex, a metal salt, a metal oxide, and the like are used.

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 becomes an acidic atmosphere and a side reaction easily occurs.

The above "alkoxy group" includes, for example, methoxy, ethoxy, n- and i-propoxy, n
-, 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) Compound (II) R ¹ in the formula (II) is an organic functional group having a fluoroalkyl group. As R ¹ , an organic functional group represented by the structural formula shown by the following formula (III) is preferable because the compound represented by the formula (II) is easy to produce and easily available.

[0019]

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, when the amount of the compound (I) exceeds 95% by weight, the water- and oil-repellency and stain resistance of the obtained cured product are liable to be reduced.

Further, the condensate of both the hydrolyzate of 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. In particular, weather resistance and water repellency
It is preferable because of good oil repellency. (3) Reactive Silicone As the reactive silicone, any compound having one or more “siloxane bond forming groups” in one molecule can be used without any 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 compounds represented by the following formulas (IV) and (V).

[0023]

Embedded image

[0024]

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 an alkyl group, a cycloalkyl group or an aryl group, respectively. R ⁴ and R
⁵ may be the same group or a different group. 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, R ⁵
The same applies to.

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).

Among them, R ³ and R ⁶ represent an alkoxy group,
When the compound is a cycloalkoxy group or an aryloxy group, these groups also function as “siloxane bond forming groups”, so that the bond between the reactive silicone and the compound (I) or the compound (II) is stronger. Can be Therefore, there is an advantage that bleeding of the unreacted reactive silicone from the cured product is reliably prevented. In particular, R ³
And R ⁶ is preferably a methoxy group, an ethoxy group, an n-propoxy group or an i-propoxy group, because these groups have good reactivity.

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 low in price 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. Such reactive silicones are inexpensive and readily available,
This is because it is easy to impart so-called “silicone properties” such as releasability, surface lubricity and water / oil repellency to the cured product.
Further, for the reason of producing the compound represented by the formula (IV), R ⁷
Is preferably an alkyl group. As the alkyl group, a methyl group, an ethyl group, an n- or i-propyl group,
An n-, i- or t-butyl group is 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 the 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. In the reactive silicone in which X 'is a halogen atom, hydrogen halide is generated by hydrolysis, so that the reaction system becomes an acidic atmosphere and a side reaction is likely to occur.

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 hydrolyzate of a compound (I), a compound (II) and a reactive silicone (hereinafter referred to as a condensate). , A hydrolyzate condensate).

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

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, a side reaction is likely to occur. In order to maintain the atmosphere of the reaction solution at pH 7 or more, an alkali agent is usually added to the system. As the alkali agent, inorganic bases such as ammonia and alkali metal hydroxide, amines, tetraalkylammonium hydroxide and the like can be used, and the activity as a basic catalyst is good, and the reaction is controlled. It is preferable to use tetraalkylammonium hydroxide because it is easy to carry out.

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, if 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. Other reaction conditions are not particularly limited, but the reaction temperature is preferably 10 to 120 ° C, more preferably 20 to 80 ° C.
C., and the reaction time is preferably 2 to 30 hours, more preferably 4 to 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, when the curable resin composition is added with a reactive diluent having radical polymerizability (hereinafter simply referred to as "reactive diluent"), the curable resin composition reduces the viscosity of the composition. It is preferable because it is easy to adjust physical properties such as hardness, mechanical strength, chemical resistance, and releasability of the cured product. (5) Reactive diluent The reactive diluent can be selected from liquid compounds having radical polymerizability, but those composed of (meth) acrylate compounds having (meth) acryloyl groups have good curability. It is preferable because the physical properties of the obtained cured product are particularly excellent.

Specific examples of the reactive diluent include (meth) acrylate of ethylene oxide-modified phenol, (meth) acrylate of propylene oxide-modified phenol, (meth) acrylate of ethylene oxide-modified nonylphenol, and (meth) acrylate of propylene oxide-modified nonylphenol. (Meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy Hexyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, Monofunctional (meth) acrylates such as ethylene glycol mono (meth) acrylate and tripropylene glycol mono (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, di (meth) acrylate of ethylene oxide-modified neopentyl glycol, di (meth) acrylate of ethylene oxide-modified bisphenol A ) Acrylate, propylene oxide-modified bisphenol A
Di (meth) acrylate, ethylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane allyl ether di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Polyfunctional (meth) acrylates such as pentaerythritol hexaacrylate, polyester acrylates such as Aronix M-6400 (polyester acrylate manufactured by Toagosei Co., Ltd.), and urethane acrylates such as Aronix M-1200 (urethane acrylate manufactured by Toagosei Co., Ltd.) No.

Among the above (meth) acrylates, trifunctional or higher functional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexaacrylate Meth) acrylate is a preferred compound for making the cured product particularly high in hardness and excellent in stain resistance.

The amount of the reactive diluent used in the curable resin composition is determined based on the nonvolatile content of the hydrolyzate condensate.
It is preferable that the amount be 5000 parts by weight or less, more preferably 5 to 3000 parts by weight, and
More preferably, it is 0 to 2000 parts by weight. If the amount of the reactive diluent exceeds 5,000 parts by weight, the proportion of the perfluoroalkyl group in the composition is reduced, so that the cured product is less likely to exhibit properties such as water repellency and oil repellency. (6) Other Components General additives such as a viscosity modifier, a leveling agent, a stabilizer, and a silane coupling agent may be added to the composition of the present invention. For the purpose of adjusting the physical properties of the cured product, a compound having a radical polymerizability (such as an unsaturated polyester) other than the hydrolyzate condensate and the reactive diluent of the present invention may be added. Further, this resin composition may contain an organic solvent, but its 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 can be cured by energy such as light, electron beam, X-ray or heat. When the curing means to be applied is light, a composition containing a photopolymerization initiator may be used. Preferably, when the curing means is heat, those containing a thermal polymerization initiator are preferred. 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.

Specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone and the like.

Specific examples of the thermal polymerization initiator include peroxides such as dicumyl peroxide and benzoyl peroxide, AIB
And azo-based polymerization initiators such as N. Specific effects exerted by the above embodiment will be described below.

According to the curable resin composition of the embodiment, since the curable resin has good compatibility with the polyfunctional (meth) acrylate, a large amount of the polyfunctional (meth) acrylate can be blended, and the basic skeleton of the obtained cured product Has a silsesquioxane structure, so that a cured product such as a coating film having a high surface hardness can be obtained.

According to the curable resin composition of the embodiment, based on the reactive diluent having radical polymerizability,
The viscosity can be adjusted to provide a composition excellent in workability such as coatability while being a solventless type, and the physical properties of the cured product can be adjusted by the type and amount of the reactive diluent used. .

According to the curable 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 curable resin composition of the embodiment, the composition is composed of, for example, a compound having a (meth) acryloyl group in which a silicone chain is partially introduced. The characteristics of silicone can be effectively imparted to the cured product without causing a problem of solubility.

According to the curable resin composition of the embodiment, since fluorine and silicone are contained in a stable state, it is possible to impart releasability to the obtained cured product.

According to the curable resin composition of the embodiment, since the composition is made of a compound having a (meth) acryloyl group, a cured product having a high surface hardness can be formed.
Therefore, the resin composition is useful, for example, as a stain-resistant paint and 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.

[0050]

The reason that the cured product of the resin composition of the present invention is excellent in stain resistance, water repellency and oil repellency and has a high surface hardness is that the hydrolyzate condensate has a silsesquie having a fluoroalkyl group. It is presumed to have an oxane structure. In addition, since the condensate has a (meth) acryloyl group, the composition of the present invention is considered to exhibit good curability.

The hydrolyzate condensate is a compound (I)
In the case of compound (II) and a reactive silicone, since a silicone chain is partially introduced,
Although the cured product has particularly excellent releasability, surface lubricity and water / oil repellency, the reason why the compatibility of the composition is good despite including the silicone component is that the silicone component of the condensate Is presumed to have been chemically bonded.

[0052]

The present invention will be described in more detail with reference to the following examples. Incidentally, the average molecular weight in the present specification,
Gel permeation chromatography (hereinafter GPC)
That. ) Is the number average molecular weight in terms of polystyrene. (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 "Acr-TRIMS". ) 44.52 g (19
0.0Mmol), a silicon compound represented by the following formula (VIII) (hereinafter, referred to as "C ₈ F ₁₇ -TRIES".) 6.11
g (10.0 mmol), N (CH ₃ ) ₄ O as a catalyst
H (10% aqueous solution) 4.55 g [H ₂ O 227.8 m
mol, N (CH ₃ ) ₄ OH 5.0 mmol], water
4.0 g (222.2 mmol) and 80.0 g of isopropyl alcohol (IPA) as a solvent were collectively charged. Then, the reaction was allowed to proceed by stirring at room temperature.

[0054]

Embedded image

[0055]

Embedded image 2) The progress of the reaction was monitored by gel permeation chromatography (GPC), and the reaction was terminated when Acr-TRIMS disappeared (about 8 hours).

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 radical-curable hydrolyzate condensate.

The obtained hydrolyzate condensate has a number-average molecular weight of about 2,000, and toluene, tetrahydrofuran (T
It was soluble in various general-purpose solvents such as HF), hexane, and acetone, and was well compatible with the reactive diluent. (2) Evaluation of curable resin composition Next, with respect to 100 parts by weight of the radical-curable hydrolyzate condensate obtained as described above, 2 parts by weight of the radical polymerization initiator [photopolymerization initiator (Trade name: Darocur 1173 manufactured by Ciba Geigy) was added to prepare a coating composition.
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 onto a glass substrate for about 20 minutes using a bar coater.
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: 10 cm, conveyor speed: 10 m
/ Min, irradiation atmosphere: in the air 2) Pencil hardness of coating film surface The coating agent is applied to a thickness of about 20 μm on a steel plate and a glass substrate using a bar coater, and the ultraviolet light (5 times) is applied under the above irradiation conditions. UV) irradiation 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 (scratch) of the coating film surface was measured according to JISK 5400.

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, tackiness of the coating agent disappeared after three irradiations of ultraviolet rays. An excellent hard coating film having a high pencil hardness of 6H on the surface of the coating film subjected to ultraviolet irradiation 5 times was able to be produced. In addition, regarding stain resistance,
It was confirmed that there was no penetration of the red ink. 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, Acr-TRIMS was used.
_{39.83g (170.0mmol), C 8 F} 17 -TR
A radical curable hydrolyzate condensate was prepared in the same manner as in Example 1 except that the IES was changed to 18.32 g (30.0 mmol). 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, tackiness of the coating agent disappeared after three irradiations of ultraviolet rays. An excellent hard coating film having a high pencil hardness of 6H on the surface of the coating film subjected to ultraviolet irradiation 5 times was able to be produced. In addition, regarding stain resistance,
It was confirmed that there was no penetration of the red ink. (Example 3) Acr-TRIMS Example 1 and C ₈ F ₁₇
To a 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 radical-curable hydrolyzate condensate. The reactive silicone used had a number average molecular weight of 2,900 and a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.38.

[0062]

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 after three irradiations of ultraviolet rays. An excellent hard coating film having a high hardness of 5H and a pencil hardness of the surface of the coating film subjected to ultraviolet irradiation 5 times was able to be produced. In addition, regarding stain resistance,
It was confirmed that there was no penetration of the red ink.

In addition, a test for an oil-resistant ink was also conducted. That is, a line was drawn with a black oil-based marker (trade name: Himackey manufactured by Zebra Co., Ltd.), and the repelling condition of the ink was visually evaluated. As a result, it was confirmed that the ink was completely repelled. Further, when a dry wiping test was performed 1,000 times with a load of 500 g, it was confirmed that the ink was repelled even after this test. In the coating 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 above-mentioned dry wiping test. It is considered that good stain resistance was maintained. (Example 4) Acr-TRIMS Example 1 and C ₈ F ₁₇
To a mixture with -TRIES, 8 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 radically curable hydrolyzate condensate. The reactive silicone used had a hydroxyl group at both terminals and a number average molecular weight of 1000 [product name: X-21-5584 manufactured by Shin-Etsu Chemical Co., Ltd.].

[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 3. As a result, the tackiness of the coating agent disappeared after three irradiations of ultraviolet rays. An excellent hard coating film having a high hardness of 5H and a pencil hardness of the surface of the coating film subjected to ultraviolet irradiation 5 times was able to be produced. In addition, regarding stain resistance,
It was confirmed that there was no penetration of the red ink and that the oil-resistant ink was completely repelled. (Example 5) Based on 50 parts by weight of the radical-curable hydrolyzate condensate obtained in Example 1, pentaerythritol triacrylate [a product of Toagosei Co., Ltd.] was used as a reactive diluent having radical polymerizability. Name: Aronix M-305] was mixed with 50 parts by weight of a radical polymerization initiator to prepare a curable resin composition. The curability, the pencil hardness of the coating film surface, and the stain resistance of the obtained curable resin composition were evaluated in the same manner as in Example 1.

As a result, the above composition lost tack after three irradiations with ultraviolet rays. An excellent hard coating film having a high pencil hardness of 6H on the surface of the coating film subjected to 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 6) Based on 50 parts by weight of the radical-curable hydrolyzate condensate obtained in Example 4, pentaerythritol triacrylate [a product of Toagosei Co., Ltd.] was used as a reactive diluent having radical polymerizability. Name: Aronix M-305] was mixed with 50 parts by weight of a radical polymerization initiator to prepare a curable resin composition. The curability, the pencil hardness of the coating film surface, and the stain resistance of the obtained curable resin composition were evaluated in the same manner as in Example 4.

As a result, tackiness of the coating agent disappeared after three irradiations of ultraviolet rays. An excellent hard coating film having a high hardness of 5H and a pencil hardness of the surface of the coating film subjected to ultraviolet irradiation 5 times was able to be produced. In addition, regarding stain resistance,
It was confirmed that there was no penetration of the red ink and that the oil-resistant ink was completely repelled.

The technical idea grasped from the above embodiment will be described below. (A) The curable 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).

[0068]

Embedded image (However, m is an integer of 0 to 10, and R ² has 1 to 1 carbon atoms.
4 alkylene group. In the case of such a constitution, the function as a fluoroalkyl group such as water / oil repellency and stain resistance can be effectively exerted, and the compound represented by the formula (II) can be easily produced and easily obtained. .

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

[0070]

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 An alkyl group,
A cycloalkyl group or an aryl group, wherein n is 1 to 10
000 is a positive number. )

[0071]

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, This is a cycloalkyl group or an aryl group, and n is a positive number of 1 to 10,000.) In this case, the cured product is repelled based on the reactive silicone represented by the formula (IV) or (V). Water and oil repellency can be improved, and the degree of crosslinking can be adjusted.

(C) The curable resin composition according to the above (b), wherein n in the formula (IV) or the formula (V) is a positive number of 10 to 100. In such a configuration, the compatibility of the reactive silicone represented by the formula (IV) or the formula (V) with other components is increased, and the transparency of the composition and the cured product can be improved.

(D) In the above formula (I) or (II), each of Xs is an alkoxy group, a cycloalkoxy group or an aryloxy group. The curable resin composition according to any one of (1) and (c).

With this configuration, the curability of the curable 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 curable resin composition according to any one of (d).

[0075]

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

The curable resin composition according to claim 1 or 2, further comprising (f) the hydrolyzate condensate and a reactive diluent having radical polymerizability. In the case of such a constitution, in addition to the effect of the invention according to claim 1 or 2, the viscosity is adjusted based on a reactive diluent having radical polymerizability, and the coatability is improved while being a solventless type. And the like, and the physical properties of the cured product can be adjusted by the type and amount of the reactive diluent used.

[0077]

As described above in detail, according to the present invention, the following excellent effects can be obtained. According to the curable resin composition of the first invention, based on a condensate of a hydrolyzate of a silane compound having a (meth) acryloyl group and a silane compound having a fluoroalkyl group, water repellency, oil repellency, and resistance to water are repelled. It is possible to obtain a cured product such as a coating film having excellent contamination properties and high hardness.

According to the curable resin composition of the second invention,
In addition to the effects of the first invention, based on a reactive silicone having one or more siloxane bond-forming groups in one molecule,
The properties of silicone can be more effectively imparted to a cured product such as a coating film.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Akira Sumi 1-Funami-cho, Minato-ku, Nagoya-shi, Aichi F-term in Nagoya Research Institute, Inc. FJ-term (reference) 4J035 BA12 CA061 CA131 CA16N CA161 LA03 LB01

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): Curable resin composition. Embedded image (However, R ⁰ is an organic functional group having an acryloyl group or a methacryloyl group, and X is a hydrolyzable group.) (However, R ¹ is a fluoroalkyl group and X is a hydrolyzable group.) 2. The curable resin composition according to claim 1, wherein the condensate of the hydrolyzate also has, as a constituent, a reactive silicone having one or more siloxane bond-forming groups in one molecule.