JPH10158404A - Production of curable resin, and curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin which comprises a (meth)acryloyl-terminated organopolysiloxane and has an improved ocmpatibility with a (meth)acrylate by subjecting an organosilicon compd. represented by the formula and a polyfunctional (meth)acrylate compd. having (meth)acryloyl groups to addition reaction. SOLUTION: An organosilicon compd. represented by the formula (wherein R<1> and R<4> are each an alkoxy, aryloxy, alkyl, cycloalkyl, or aryl, pref. R<1> is an alkoxy or aryloxy, still pref. R<1> and R<4> are both an alkoxy or aryloxy; R<2> and R<3> are each an alkyl, cyclalkyl, or aryl, pref. R<2> and R<3> are both CH3 ; and n is 0-100, pref. 1-50, still pref. 3-30) and a polyfunctional (meth)acrylate compd. having at least two (meth)acryloyl groups (e.g. trimethylolpropane PO- modified triacrylate) are subjected to addition reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a curable resin and a curable resin composition. Curable resin composition using the resin obtained by this manufacturing method, transparency,
Excellent gloss, peelability, surface lubricity and water / oil repellency,
It is useful as a release paper resin, a coating agent, a corrosion inhibitor for printed circuit boards, and the like.

[0002]

2. Description of the Related Art Curable resins composed of organopolysiloxanes having (meth) acryloyl groups at the terminals and / or side chains are excellent in polymerization reactivity and UV curability, and are used for release paper resins, coating agents and prints. It is used as a corrosion inhibitor for substrates. As a method for producing such a curable resin, there is known a method in which an organopolysiloxane having a SiH group and a (meth) acrylate compound having a plurality of (meth) acryloyl groups are subjected to a hydrosilylation reaction in the presence of a platinum catalyst. (Journal of
Applied Polymer Science 47, 1309-1314 (1993
Year) ).

[0003]

However, in the above method, a dimethylsiloxane-methylhydrogensiloxane copolymer represented by the following formula (II) (hereinafter referred to as "PDMHMS") is referred to as "organopolysiloxane having a SiH group". "
That. ) Is used.

[0004]

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Therefore, what is obtained by this method is
A curable resin comprising an organopolysiloxane having a (meth) acryloyl group in a side chain, and a (meth) terminal
It does not have an acryloyl group. The raw material P
Since DMHMS is a copolymer, the number and position of SiH groups present in one molecule vary widely. For this reason,
It is difficult to control the reaction during the hydrosilylation reaction, and it is also difficult to control the performance of the obtained curable resin.

[0006] Furthermore, the PDMHMS used in the above method has a low compatibility with the (meth) acrylate compound, so that a relatively large amount of a catalyst is required for the hydrosilylation reaction to proceed sufficiently. In particular, when trimethylolpropane triacrylate (hereinafter, referred to as "TMPTA") is used as the (meth) acrylate compound, it is necessary to use an organic solvent in addition to a large amount of a catalyst. Further, since the obtained curable resin is generally cloudy, it may be inconvenient to use it as, for example, a coating material.

An object of the present invention is to provide a method for producing a curable resin comprising an organopolysiloxane having a terminal (meth) acryloyl group and having improved compatibility with a (meth) acrylate compound. Another object of the present invention is to provide a curable resin composition comprising a curable resin obtained by this production method.

[0008]

The present inventors have found that α, ω having a relatively small molecular weight and having a hydrogen atom at the terminal silicon.
The present inventors have found that the above problems can be solved by using a polysiloxane, and completed the present invention.

That is, the method for producing the curable resin of the first invention according to the present invention is a method for producing a polyfunctional compound having two or more (meth) acryloyl groups in an organosilicon compound represented by the following structural formula (I). It is characterized by adding a (meth) acrylate compound.

[0010]

Embedded image (Where R ¹ and R ⁴ are respectively an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group or an aryl group, R ² and R ³ are each an alkyl group, a cycloalkyl group or an aryl group, and n is It is a positive number from 0 to 100.)

According to the production method of the first invention, a curable resin comprising an organopolysiloxane having at least one (meth) acryloyl group at both terminals can be obtained. The compound represented by the above formula (I) has two Si atoms per molecule.
Since there is only an H group, the hydrosilylation reaction occurs only at both ends of the compound represented by the above formula (I). Therefore, PDMHMS in which many SiH groups can exist in one molecule
There is an advantage that the structure of the obtained curable resin and the cured product thereof can be easily designed, as compared with the above-mentioned conventional method using. N in the above formula (I) is a relatively small value of 0 to 100. This has the effect of improving the compatibility between this compound and the curable resin produced therefrom and the (meth) acrylate compound. In particular, when n is 1 to 50 as in the fourth invention, the effect is large.

Further, the method of the present invention for producing a curable resin according to the second invention is characterized in that, in the production method of the first invention, R ¹ in the above formula (I) is an alkoxy group or an aryloxy group. . That is, the compound represented by the above formula (I) is an α, ω-type polysiloxane in which the terminal silicon has at least one alkoxy group and / or aryloxy group. The alkoxy group and / or aryloxy group bonded to the terminal silicon has an effect of improving the compatibility between the compound represented by the formula (I) and the curable resin produced from the compound and the (meth) acrylate compound. . In particular, according to the third aspect of the present invention, wherein R ¹ and R ⁴ in the above formula (I) are both an alkoxy group or an aryloxy group, the effect of improving compatibility is further enhanced, which is preferable.

The curable resin composition of the fifth invention according to the present invention is characterized by comprising the curable resin produced by the method of the first invention to the fourth invention and a (meth) acrylate compound. This "(meth) acrylate compound"
The polyfunctional (meth) acrylate compound used in the production of the curable resin may be used, or another (meth) acrylate compound may be used. Since the curable resin produced by the method of the present invention has improved compatibility with the (meth) acrylate compound, the curable resin composition mixed with the (meth) acrylate compound in order to adjust the viscosity and performance. Can also be suitably used.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In this specification, acrylate and / or methacrylate are referred to as (meth) acrylate, and acryloyl and / or methacryloyl groups are referred to as (meth) acryloyl group. The method for producing a curable resin according to the first invention in the present invention is characterized in that an organosilicon compound represented by the above formula (I), that is, an α, ω-type polysiloxane having a terminal Si—H group and a relatively small molecular weight, A polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups is added.

First, the "organosilicon compound represented by the formula (I)" will be described. In the above formula (I), R ¹ and R ⁴ are each an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group or an aryl group. Examples of the "alkoxy group" include a methoxy group, an ethoxy group, n- and i-propoxy groups, n-, i- and t-butoxy groups, and examples of the "aryloxy group" include a phenoxy group and the like. Is mentioned. Examples of the “alkyl group” include a methyl group, an ethyl group, n- and i-propyl groups, n-, i- and t-butyl groups, and examples of the “cycloalkyl group” include a cyclohexyl group. Examples of the “aryl group” include a phenyl group.
One molecule of the compound represented by the formula (I) contains two R ^{1 s,} which may be the same or different. In addition, two Rs contained in one molecule
⁴ may be the same group or a different group. Further, R ¹ and R ⁴ may be the same group or different groups.

In the above formula (I), R ² and R
³ is an alkyl group, a cycloalkyl group or an aryl group, respectively. As the “alkyl group”, “cycloalkyl group” and “aryl group”, those exemplified in the description of R ¹ and R ⁴ can be used. still,
R ² and R ³ may be the same group or different groups. Further, n R ² contained in one molecule may be the same group or two or more different groups,
The same applies to R ³ .

In the present invention, R ¹ is preferably an alkoxy group or an aryloxy group as in the second invention, and both R ¹ and R ⁴ are an alkoxy group or an aryloxy group as in the third invention. It is even more preferred.
In this case, since the terminal silicon has two groups selected from an alkoxy group and an aryloxy group in addition to the hydrogen atom, the compound represented by the above formula (I) and the curable resin produced therefrom This is because compatibility with the (meth) acrylate compound is greatly improved.

R ^{1 to} R ⁴ in the above formula (I) may be appropriately selected according to the required performance of the curable resin or the curable resin composition to be obtained. Of these, R ² and R
^When a compound in which ³ is a methyl group or an ethyl group is used, this compound can be produced from inexpensive raw materials, and here, the so-called “silicone of releasability, surface lubricity and water / oil repellency” is used. Compounds in which R ² and R ³ are all methyl groups are preferable because they easily impart “characteristics”. Further, when two R ¹ and two R ⁴ present in one molecule are the same group, it is preferable because the synthesis of this compound is easy, and further, R ¹ and R ⁴ are the same group. Is more preferable. Also, R ¹ and R ⁴
When is an ethoxy group, there is an advantage that the toxicity of this compound is low.

In the above formula (I), n is a positive number from 0 to 100. When n exceeds 100, the compatibility between this compound and the resulting curable resin and the (meth) acrylate compound is reduced, and a large amount of a catalyst or a solvent is required to allow the reaction to proceed sufficiently, or the This causes a disadvantage that the cured resin becomes cloudy. From the viewpoint of compatibility with the (meth) acrylate compound, n is preferably at most 50, more preferably at most 30. In order to impart the properties of silicone to the obtained curable resin, n is preferably 1 or more, and more preferably 3 or more.

The compound in which R ¹ and R ⁴ in the above formula (I) are both an alkoxy group or an aryloxy group can be prepared, for example, by the reaction formula shown in the following formula (III), that is, polysiloxane-α, ω- It can be obtained by a dealcoholization (or phenol) reaction between a diol and a trialkoxy (or aryloxy) silane. This reaction is preferably performed under conditions in which the trialkoxy (or aryloxy) silane is in excess. During the reaction, p-
A transesterification catalyst such as toluenesulfonic acid or trifluoroacetic acid may be used, or a transesterification catalyst may not be used.

[0021]

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Next, the "polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups" to be added to the compound represented by the formula (I) will be described. Examples of the polyfunctional (meth) acrylate compound include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene 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, 1,5-pentanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth)
Acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol ethylene oxide (hereinafter, “ethylene oxide” is referred to as EO), modified di (meth) acrylate, neopentyl glycol propylene oxide (hereinafter, “propylene oxide” is referred to as PO) Modified di (meth) acrylate, bisphenol A EO modified di (meth) acrylate, bisphenol A PO modified di (meth) acrylate, hydrogenated bisphenol A EO modified di (meth) acrylate, hydrogenated bisphenol A PO modified di (meth) acrylate , Trimethylolpropane di (meth) acrylate, trimethylolpropane EO-modified di (meth) acrylate, trimethylolpropane PO-modified di (meth) acrylate, glycerin di (meth) acryl Rate, glycerin EO-modified di (meth) acrylate, glycerin PO-modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, trimethylolpropane PO
Modified tri (meth) acrylate, glycerin tri (meth) acrylate, glycerin EO modified tri (meth) acrylate, glycerin PO modified tri (meth) acrylate, pentaerythritol EO modified tetra (meth) acrylate, pentaerythritol PO modified tetra (meth) acrylate Acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol EO modified tri (meth) acrylate, pentaerythritol PO modified tri (meth) acrylate, dimethylolpropane tri (meth) acrylate and trimethylol And propane allyl ether di (meth) acrylate. In addition to these, any compound having two or more (meth) acryloyl groups can be used without any particular limitation, but a compound having no hydroxyl group in the molecule is preferable.

Of these, trimethylolpropane PO-modified triacrylate and trimethylolpropane allyl ether diacrylate are preferably used. These polyfunctional (meth) acrylate compounds have the formula (I)
This is because the compatibility with the compound shown in (1) and the obtained curable resin is particularly good.

Next, a method of "adding" a polyfunctional (meth) acrylate compound to the compound represented by the above formula (I) will be described. This is due to the presence of S at both ends of the compound.
A hydrosilylation reaction between an i-H group and a (meth) acryloyl group of a polyfunctional (meth) acrylate compound, which proceeds in the presence of a Group VIII metal catalyst or the like. This "Eighth
Examples of the "group metal catalyst" include a simple substance of a group VIII metal such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum, an organic metal complex, a metal salt, and a metal oxide. Of these, simple platinum metals, organometallic complexes, metal salts and metal oxides are preferred, and organic platinum complexes are particularly preferred, for reasons such as high catalytic activity and ease of handling. This catalyst is preferably used in an amount of 0.1 to 5% by weight based on the total amount of the compound represented by the formula (I) and the polyfunctional (meth) acrylate compound. The other reaction conditions in the hydrosilylation reaction are not particularly limited, but the preferred reaction temperature is 2
0 to 80 ° C., and a suitable reaction time is 2 to 10 hours.

When a compound having three acryloyl groups is used as the polyfunctional (meth) acrylate compound, examples of the curable resin formed by the hydrosilylation reaction are represented by the following formulas (IV) and (V). Is shown.

[0026]

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At this time, there is a possibility that the curable resin represented by the above formula (IV) and the curable resin represented by the above formula (V) may be produced at the same time. And the polyfunctional (meth) acrylate compound can be adjusted by the charging ratio and the like. For example, the presence of a polyfunctional (meth) acrylate compound in an excess (preferably a large excess) with respect to the Si—H group of the compound represented by the above formula (I) allows the compound of the above formula (IV) to be mainly produced. Is obtained. It is preferable to carry out the reaction under such a condition that the polyfunctional (meth) acrylate compound becomes excessive from the viewpoint of suppressing gelation during the reaction.

Since the curable resin produced by the above method has one or more (meth) acryloyl groups at both ends, it can be cured by heat, ultraviolet light, electron beam or the like. Further, since the main chain of the curable resin is composed of siloxane bonds, it is possible to obtain a cured product exhibiting silicone properties such as releasability, surface lubricity, and water / oil repellency. Further, since the molecular weight is relatively low, the compatibility with the (meth) acrylate compound is higher than that of a resin having a higher molecular weight. Accordingly, it is easy to produce a curable resin, and a cured film having high transparency and gloss can be obtained from the curable resin or a curable resin composition in which various (meth) acrylate compounds are blended. . In particular, when the terminal silicon of the siloxane chain has an alkoxy group and / or an aryloxy group as in the second invention, the compatibility with the (meth) acrylate compound is larger than that of a resin having no such group. There is an effect of improving. Before or after the curing of the resin, the alkoxy group and / or the aryloxy group can be used for further reaction.

The curable resin composition according to the fifth invention of the present invention comprises the curable resin produced by the above method and (meth)
It consists of an acrylate compound. The “(meth) acrylate compound” in the fifth invention includes phenol-EO-modified (meth) acrylate, phenol-PO-modified (meth) acrylate, nonylphenol-EO-modified (meth) acrylate, nonylphenol-PO-modified (meth)
Acrylate, 2-ethylhexyl carbitol (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth)
Acrylate, hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) acrylate,
Dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, 1,
4-butanediol mono (meth) acrylate, 1,5
-Pentanediol mono (meth) acrylate, 1,6
-Hexanediol mono (meth) acrylate, 1,9
-Nonanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, neopentyl glycol EO-modified mono (meth) acrylate, neopentyl glycol PO-modified mono (meth) acrylate, bisphenol A EO-modified mono (meth) acrylate, Bisphenol A PO-modified mono (meth) acrylate, hydrogenated bisphenol A EO-modified mono (meth)
Acrylate, hydrogenated bisphenol A PO-modified mono (meth) acrylate, and the like.
The above polyfunctional (meth) acrylate compounds described in connection with the invention can be used. Of these, only one kind may be used, or two or more kinds may be used in combination.

In the curable resin composition, the mixing ratio of the curable resin and the (meth) acrylate compound varies depending on the purpose of use, and is not particularly limited.
The mixing ratio of the curable resin to 100 parts by weight of the (meth) acrylate compound is preferably 0.1 to 90 parts by weight, and particularly preferably 1 to 50 parts by weight. If the proportion of the curable resin is less than 0.1 part by weight, the surface lubricity of the cured product may be insufficient, and if the proportion of the curable resin exceeds 90 parts by weight, the hardness of the cured product decreases. There is fear.

The method of curing the curable resin composition in the present invention is not particularly limited, but it is preferable to carry out thermal curing, ultraviolet curing and electron beam curing. As a specific method therefor, these usual curing means can be directly applied.

[0032]

The present invention will now be described more specifically with reference to examples and comparative examples.

(1) Production of curable resin and curable resin composition (Synthesis Example 1) This is an example of synthesizing an organosilicon compound represented by the above formula (I) as a raw material of a curable resin.
According to the reaction formula shown in the following formula (1), both R ¹ and R ⁴ in the above formula (I) are ethoxy groups, both R ² and R ³ are methyl groups, and n is about 18 A certain α, ω-type polydimethylsiloxane (hereinafter referred to as “silicone A”) was synthesized.

[0034]

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The raw materials used are as follows. [Raw materials] (1) Polydimethylsiloxane-α, ω-diol (manufactured by Dow Corning Toray Silicone Co., Ltd., number average molecular weight 1,272 (in terms of polystyrene)) (2) Triethoxysilane (manufactured by Toagosei Co., Ltd. Product name "Tries")

Hereinafter, the reaction operation will be described. A 100 ml four-necked flask equipped with a stirrer, a thermometer, and a cooler was charged with 10.0 g (7.9 mmol) of polydimethylsiloxane-α, ω-diol, and after degassing under vacuum, the system was purged with nitrogen. The reactor was heated to 60 ° C and triethoxysilane 1
5.0 g (92 mmol) was added, and the reaction was allowed to proceed while stirring at 60 ° C. The progress of the reaction was followed by gas chromatography. After 6 hours, it was confirmed that the composition ratio of the raw material triethoxysilane and the by-produced ethanol had not changed, and the reaction was terminated. Excess triethoxysilane and by-produced ethanol were removed from the obtained reaction solution under reduced pressure. Further, under a heated vacuum atmosphere (60 to 70 ° C., 0.01 torr), volatile impurities are removed, and a colorless and transparent viscous liquid is obtained.
8 g were obtained.

The obtained substance was identified as 2, in the IR chart.
A peak indicating the presence of a hydrogen atom bonded to terminal silicon was observed at around 200 cm ^-1 . The NMR of this material
In the chart, a peak at 3.8 ppm (corresponding to a hydrogen atom (Si—OCH ₂ —) bonded to a carbon atom adjacent to oxygen in an ethoxy group bonded to the terminal silicon)
From the ratio of the peak area of the peak at 4.7 ppm (corresponding to the hydrogen atom bonded to the terminal silicon (Si—H)), the ratio of the number of ethoxy groups bonded to the terminal silicon to the number of hydrogen atoms was determined. It turned out to be 2: 1. From the above, R ¹ and R ⁴ in the above formula (I) are ethoxy groups,
It was confirmed that silicone A in which ² and R ³ were methyl groups was synthesized.

(Example 1) Silicone A obtained in Synthesis Example 1
Then, a curable resin (hereinafter, referred to as "acrylic silicone resin A-1") was produced by adding trimethylolpropane PO-modified triacrylate according to the reaction formula shown in the following formula (2).

[0039]

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Hereinafter, the reaction operation will be described. In a 100 ml reactor equipped with a stirrer, thermometer and condenser, 3.0 g (2.1 mmol) of silicone A, P
30.0 g (63.8 mmol) of trimethylolpropane PO-modified triacrylate having 1 mole of O added (trade name “Aronix M-310” manufactured by Toagosei Co., Ltd.)
After charging and vacuum degassing, the inside of the system was replaced with nitrogen. After the temperature of the system was raised to 70 to 80 ° C., PtCl ₂ (C ₆
H ₅ CN) ₂ in 0.05M benzonitrile
The reaction was allowed to proceed by stirring while maintaining the inside of the system at 70 to 80 ° C. After 6 hours, by removing volatile substances such as benzonitrile in a heated vacuum atmosphere, a slightly yellow transparent curable resin composition comprising acrylic silicone resin A-1 and excess trimethylolpropane PO-modified triacrylate The product B-1 was obtained.

(Example 2) A trimethylolpropane PO-modified triacrylate having a different PO addition mole number from that of Example 1 was added to the silicone A obtained in Synthesis Example 1 to form a curable resin (hereinafter referred to as " Acrylic silicone resin A
-2 ". ) Manufactured. That is, in Example 2, trimethylolpropane P having 1 mole of PO addition was used.
Instead of the O-modified triacrylate, a PO-modified trimethylolpropane PO-modified triacrylate (trade name “ARONIX M-32” manufactured by Toagosei Co., Ltd.) was used instead of the O-modified triacrylate.
0 ") 30.0 g (46.5 mmol) were used. Otherwise in the same manner as in Example 1, a slightly yellow transparent curable resin composition B-2 comprising an acrylic silicone resin A-2 and an excess of trimethylolpropane PO-modified triacrylate was obtained.

(Example 3) Silicone A obtained in Synthesis Example 1
Was added with trimethylolpropane allyl ether diacrylate to produce a curable resin (hereinafter referred to as "acrylic silicone resin A-3"). That is, in Example 3, the PO addition mole number 1 used in Example 1 was used.
Was replaced by 30.0 g (106.3 mmol) of trimethylolpropane allyl ether diacrylate.
Otherwise in the same manner as in Example 1, a slightly yellow transparent curable resin composition B-3 comprising an acrylic silicone resin A-3 and an excess of trimethylolpropane PO-modified triacrylate was obtained.

(Comparative Example 1) The polydimethylsiloxane-α, ω-diol used in Synthesis Example 1 had a number average molecular weight of 1,272, but instead had a high number average molecular weight of about 10,000. Dimethylsiloxane-α, ω-
A diol was used. Otherwise in the same manner as in Synthesis Example 1, R ¹ and R ⁴ are ethoxy groups, and R ² and R 4
^An α, ω-type polydimethylsiloxane (hereinafter, referred to as “silicone a”) in which ³ is a methyl group and n is about 130 was synthesized. Trimethylolpropane PO-modified triacrylate (P) was prepared in the same manner as in Example 1 except that silicone a having a high molecular weight was used in place of silicone A.
1) was added to obtain a slightly yellowish cloudy curable resin composition b-1 consisting of an acrylic silicone resin a-1 and an excess of trimethylolpropane PO-modified triacrylate.

(2) Evaluation of the curable resin composition The curable resin compositions obtained in Examples 1 to 3 and Comparative Example 1 and the above-mentioned “Aronix M-310” and “Aronix M-320” were photoinitiators. Add 3wt%,
The ultraviolet curability and the peelability of the cured film were evaluated. still,
As the photoinitiator, 2-hydroxy-2-methyl-1-
Phenyl-propan-1-one (trade name “Darocure 1173” manufactured by Ciba Geigy Corporation) was used.

[Film formation method] Substrate: polycarbonate Coating method: 20 μm bar coating [Ultraviolet irradiation condition] Lamp: 80 W / cm condensing high pressure mercury lamp Lamp height: 10 cm Conveyor speed: 10 m / min

[Curability] Under the above-mentioned irradiation conditions, the film was repeatedly passed under an ultraviolet lamp 10 times, and the cured state was evaluated. The evaluation results were expressed in the following four stages. ；: Good (no surface tack) ○: Almost good (slight surface tack) △: Slightly poor (surface tack) ×: Not cured [Releasability] Apply adhesive tape to the surface of cured film by hand, immediately after ＝= weak (high releasability), Δ = medium, × = strong (low releasability) according to the strength of the force required when peeling by hand. Table 1 shows the evaluation results.

[0047]

[Table 1]

As can be seen from Table 1, the curable resin compositions of Examples 1 to 3 all had good or almost good curability. Also in the composition of Example 3, it was possible to cure until the surface tack disappeared by further passing under the lamp five times. Further, since the curable resin composition and the cured film thereof are transparent, the curable resins A-1 to A-1.
It can be seen that A-3 has good compatibility with (meth) acrylate compounds such as M-310, M-320, and TMPAEDA. Since the cured films obtained from the compositions of Examples 1 to 3 are provided with the properties of silicone by the curable resins A-1 to A-3, the cured films composed of only M-310 or M-320 can be used. In comparison, the releasability was remarkably excellent.
In addition, it is considered that acryloyl groups have been introduced into at least most of the silicones because of good curability and no bleeding or the like on the surface of the cured film.

On the other hand, in Comparative Example 1 using a high-molecular-weight silicone, the compatibility between the curable resin a-1 and M-310 was insufficient, so that both the composition b-1 and the cured film thereof were not used. It was cloudy. Silicon bleeds on the surface of the cured film, indicating that the silicone having no acryloyl group introduced therein remains. When the curable resin composition b-1 was left for one day, the lower layer mainly composed of an excess of trimethylolpropane PO-modified triacrylate and the upper layer mainly composed of acrylic silicone resin a-1 and slightly yellowish and turbid. And separated into

It should be noted that the present invention is not limited to the specific embodiments described above, but can be variously modified within the scope of the present invention depending on the purpose and application.

[0051]

The curable resin according to the production method of the present invention comprises:
It can be cured by heat, ultraviolet rays, electron beams, etc., and the cured product has peelability, surface lubricity and water repellency.
Excellent "silicone properties" such as oil repellency. In addition, since the compatibility with the (meth) acrylate compound is good, the above-mentioned silicone can be obtained from the curable resin produced by the method of the present invention or the curable resin composition of the present invention in which the (meth) acrylate compound is blended. In addition to the characteristics, a cured film having high transparency and gloss can be obtained. Therefore, it is useful as a release paper resin, a coating agent, a corrosion inhibitor for printed circuit boards, and the like.

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[Procedure amendment]

[Submission date] October 8, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

[0026]

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[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

[0039]

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 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Takehisa Hattori 1 in Funami-cho, Minato-ku, Nagoya-shi, Aichi, Japan

Claims (5)

[Claims] 1. A curable composition comprising a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups added to an organosilicon compound represented by the structural formula shown in the following formula (I). Method of manufacturing resin. Embedded image (Where R ¹ and R ⁴ are respectively an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group or an aryl group, R ² and R ³ are each an alkyl group, a cycloalkyl group or an aryl group, and n is It is a positive number from 0 to 100.) 2. The method according to claim 1, wherein R ¹ in the formula (I) is an alkoxy group or an aryloxy group. 3. The method according to claim 2, wherein R ⁴ in the formula (I) is an alkoxy group or an aryloxy group. 4. The formula (I) according to claim 1, wherein n is 1
The method for producing a curable resin according to claim 1, 2 or 3, which is a positive number of from 50 to 50. 5. A curable resin composition comprising a curable resin produced by the method according to claim 1 and a (meth) acrylate compound.