JP6021605B2 - Cage type silsesquioxane compound, curable resin composition and resin cured product using the same - Google Patents

Description

  The present invention relates to a cage silsesquioxane compound, a curable resin composition using the same, and a cured resin product.

  Generally, a glass plate is widely used as a transparent substrate such as a substrate for a liquid crystal display element, a substrate for a color filter, a substrate for an organic EL display element, a substrate for electronic paper, a substrate for TFT, or a substrate for solar cell. However, in recent years, the use of a transparent plastic plate as an alternative has been studied because glass plates are easily broken, difficult to bend, and have a large specific gravity and are not suitable for weight reduction.

  On the other hand, silsesquioxane having a cage structure has attracted attention in various fields because it can express a specific function by utilizing its characteristic structure. In particular, a cured product of a cage-type silsesquioxane resin is expected as a material for a transparent plastic plate that can be used as a substitute for a glass plate because it has excellent heat resistance, weather resistance, optical properties, dimensional stability, and the like.

As a cured product of such a cage silsesquioxane resin, for example, in Japanese Patent Application Laid-Open No. 2006-89685 (Patent Document 1), it is represented by [RSiO _3/2 ] _n , and a (meth) acryloyl group is functionalized. A silicone resin copolymer obtained by radical copolymerization of a silicone resin composition containing a cage-type polyorganosilsesquioxane, an oligomer and an unsaturated compound as a group is described.

In JP 2004-143449 A (Patent Document 2), a cage type represented by [RSiO _3/2 ] _n and having any one of a (meth) acryloyl group, a glycidyl group, and a vinyl group. Silsesquioxane resins are disclosed.

JP 2006-89685 A JP 2004-143449 A

  Although the silicone resin copolymer described in Patent Document 1 has a somewhat small linear expansion coefficient in a non-water-absorbing state, a (meth) acryloyl group which is a hydrophilic group on all silicon atoms in the skeleton Since it is obtained using a cage silsesquioxane compound (cage polyorganosilsesquioxane) having a high water absorption, it has a problem that the coefficient of linear expansion increases due to water absorption. The present inventors have found that.

  Further, the cage-type polyorganosilsesquioxane described in Patent Document 1 and the cage-type silsesquioxane having a (meth) acryloyl group among the cage-type silsesquioxane resins described in Patent Document 2 above. Although it becomes possible to obtain a cured resin having excellent transparency by using an oxan resin, the obtained cured resin is not sufficient in weather resistance, and when exposed to ultraviolet rays having a wavelength of about 300 nm for a long time. The present inventors have found that there arises a problem that the color is changed to yellow and transparency is lowered.

  The present invention has been made in view of the above-mentioned problems of the prior art, and is a curable resin composition having excellent moldability, and has excellent transparency and low water absorption and excellent weather resistance. It is an object of the present invention to provide a cage silsesquioxane compound capable of obtaining a cured resin product, a curable resin composition using the same, and a cured resin product obtained by curing the same.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a novel cage silsesquioxane compound having a (meth) acryloyl group and a reactive organic functional group containing a specific hydrocarbon chain. By using it, a curable resin composition having excellent moldability can be obtained, and a cured resin obtained by curing the composition has excellent transparency and low water absorption, and also has good weather resistance. The present invention has been found to be excellent, and the present invention has been completed.

That is, the cage silsesquioxane compound of the present invention is
The following general formula (1):
[R ¹ SiO _3/2 ] _n [R ² SiO _3/2 ] _m [R ³ SiO _3/2 ] _j (1)
{In formula (1), R ¹ is the following general formula (2):

[In Formula (2), R ⁴ represents a hydrogen atom or a methyl group, and p represents an integer of 4 to 10. ]
R ² represents the following general formula (3):

[In Formula (3), R ⁵ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 3. ]
A group represented by the following general formula (4):

[In Formula (4), r shows the integer of 1-3. ]
A group represented by the following general formula (5):

[In Formula (5), s shows the integer of 1-3. ]
And a group represented by the following formula (6):

Any one group selected from the group consisting of the groups represented by: R ³ is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and an allyl group; N, m and j are the following formulas (i) to (iv):
n ≧ 2 (i),
m ≧ 1 (ii),
j ≧ 0 (iii),
n + m + j = h (iv)
[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]
When n, m and j are each 2 or more, R ¹ , R ² and R ³ may be the same or different. }
It is characterized by being represented by.

  The curable resin composition of the present invention contains the cage silsesquioxane compound of the present invention and a radical polymerization initiator, and the content of the cage silsesquioxane compound is 10 to 80. It is characterized by being mass%.

The curable resin composition preferably further contains an unsaturated compound having a (meth) acryloyl group other than the cage silsesquioxane compound, ladder siloxane, and random siloxane. In addition, the curable resin composition is cast so as to have a thickness of 0.2 mm, and radical polymerization is performed at room temperature using a high-pressure mercury lamp with an illuminance of 30 W / cm by light irradiation with an integrated exposure amount of 2000 mJ / cm ^2. At the time of caulking, the reaction rate of the (meth) acryloyl group measured by infrared spectroscopy is preferably 70% or more. Furthermore, as said curable resin composition, it is preferable that content of the said radical polymerization initiator is 0.01-10 mass%.

Cured resin of the present invention is characterized in that said a radical polymer of the curable resin composition of the present invention.

  The reason why the object is achieved by the configuration of the present invention is not necessarily clear, but the present inventors infer as follows. That is, it has been conventionally known that a compound having a (meth) acryloyl group is generally excellent in radical polymerizability. However, when producing a cured resin using a resin composition containing a cage-type silsesquioxane compound having a (meth) acryloyl group as described in Patent Documents 1 and 2, the compound Some (meth) acryloyl groups may remain as unreacted groups. If a large amount of such unreacted groups (residual double bonds) remain in the resin cured product, bond breakage or recombination may occur due to exposure to high temperatures in the presence of oxygen or external exposure to ultraviolet rays for a long time. The present inventors speculate that this causes cracking and yellowing.

  In contrast, the cage silsesquioxane compound of the present invention has a sufficiently large flexibility because it has a reactive organic functional group containing a specific hydrocarbon chain together with a (meth) acryloyl group, And it is excellent in radical polymerizability. Therefore, in the resin cured product of the present invention obtained by using this, the remaining unreacted groups are sufficiently reduced, and the present inventors speculate that excellent weather resistance is exhibited together with excellent transparency. .

  Furthermore, in the curable resin composition containing the cage silsesquioxane compound of the present invention having the specific reactive organic functional group as described above, the content ratio of the (meth) acryloyl group which is a hydrophilic group is Since it is sufficiently reduced, the present inventors infer that the obtained resin cured product also exhibits excellent low water absorption.

In the present invention, the (meth) acryloyl group means an acryloyl group and a methacryloyl group. In the present invention, the reaction rate of the (meth) acryloyl group is the rate of change of the double bond of the (meth) acryloyl group when the curable resin composition containing a compound having a (meth) acryloyl group is cured. Noboru Ohara et al., “Material Design / Coating Technology and Hardness Improvement in Hard Coat Films Focusing on Plastic Substrates”, Technical Information Association, April 28, 2005, p136-139 It can be determined according to the method described. More specifically, first, the resin composition is cast so as to have a thickness of 0.2 mm, and light irradiation with an integrated exposure amount of 2000 mJ / cm ² is performed at room temperature using a high-pressure mercury lamp with an illuminance of 30 W / cm. before and after allowed to radical polymerization in the range of 1723～1735Cm ^-1 (preferably 1728 cm ^-1) of (meth) carbons in acryloyl groups by - maximum absorbance derived from stretching vibration of oxygen double bonds (C = O) ( A _{C = O} ) and the maximum absorbance derived from the stretching vibration of the carbon-carbon double bond (C = C) in the (meth) acryloyl group of 1627 to 1638 cm ^-1 (preferably 1635 cm ^-1 ) (A _{C = C 1} ) is measured using a microinfrared spectrometer. Next, the ratio of A _C═O (AW _C═O ) to A _C═C (AW _{C = C} ) in the resin composition before radical polymerization (AW = AW _{C═O 2} / AW _{C = C} ), and From the ratio (AF = AF _{C = O 2} / AF _{C = C} ) of A _C═O (AF _C═O ) and A _{C = C} (AF _{C = C} ) in the cured resin after polymerization, the following formula :
Double bond change rate (A _R ) = (1−AW / AF) × 100
Thus, the double bond change rate (A _R (%)) of the (meth) acryloyl group, that is, the reaction rate of the (meth) acryloyl group can be obtained.

  According to the present invention, a curable resin composition having excellent moldability, and a cage-type silsesquic that can provide a cured resin having excellent transparency and low water absorption and excellent weather resistance. It becomes possible to provide an oxan compound, a curable resin composition using the oxan compound, and a cured resin obtained by curing it.

4 is a graph showing the GPC result of the resin mixture 1 obtained in Synthesis Example 1. 4 is a graph showing the results of mass spectrometry of a resin mixture 1 obtained in Synthesis Example 1. 6 is a graph showing a GPC result of a resin mixture 2 obtained in Synthesis Example 2. 6 is a graph showing a GPC result of a resin mixture 3 obtained in Synthesis Example 3. 6 is a graph showing a GPC result of a resin mixture 4 obtained in Synthesis Example 4. 6 is a graph showing a GPC result of a resin mixture 5 obtained in Synthesis Example 5. 6 is a graph showing a GPC result of a resin mixture 6 obtained in Synthesis Example 6. 6 is a graph showing a GPC result of a resin mixture 7 obtained in Synthesis Example 7. 6 is a graph showing a GPC result of a resin mixture 8 obtained in Synthesis Example 8.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

First, the cage silsesquioxane compound of the present invention will be described. The cage silsesquioxane compound of the present invention has the following general formula (1):
[R ¹ SiO _3/2 ] _n [R ² SiO _3/2 ] _m [R ³ SiO _3/2 ] _j (1)
It is characterized by being represented by.

In the formula (1), R ¹ is a reactive organic functional group containing a (meth) acryloyl group which is a radical polymerizable functional group and a hydrocarbon chain, and the following general formula (2):

The group represented by these is shown. In the formula (2), R ⁴ represents a hydrogen atom or a methyl group. As R ⁴ , a methyl group is particularly preferable from the viewpoint that the water absorption of the obtained resin cured product can be further reduced by the repulsion effect of the three-dimensional structure.

In the above formula (2), p represents an integer of 4 to 10, and the hydrocarbon chain represented by (CH ₂ ) _p may be linear or branched. From the viewpoint of being easy, it is preferably linear. If the value of p is less than the lower limit, the number of (meth) acryloyl groups per unit weight will increase, resulting in a deterioration in the water absorption of the resulting cured product. On the other hand, if the upper limit is exceeded, the hydrocarbon chain Since the length becomes too long, the resulting cured product may be decomposed or yellowed when exposed to ultraviolet rays for a long time. As such p, from the viewpoint that the raw materials are easily available, the flexibility (degree of freedom) of the cage silsesquioxane compound is greater, and the radical polymerizability is further improved. Is preferably an integer of 8, more preferably 8, and the hydrocarbon chain is particularly preferably an octylene group.

In the formula (1), R ² represents any one group selected from the group consisting of groups represented by the following general formulas (3) to (6).

In the formula (3), R ⁵ represents a hydrogen atom or a methyl group, and is a methyl group from the viewpoint that the water absorption of the obtained cured resin can be further reduced by the repulsive effect of the three-dimensional structure. Particularly preferred. Moreover, in said Formula (3)-(5), q, r, and s show the integer of 1-3 each independently, and it is more preferable that it is 3. If the values of q, r, and s are less than the lower limit, it tends to be difficult to obtain the raw material. On the other hand, if it exceeds the upper limit, the hydrocarbon represented by (CH ₂ ) _t (t is q, r, or s). Since the chain becomes too long, the resulting cured product tends to cause deterioration such as deterioration and yellowing when exposed to ultraviolet rays for a long time. The hydrocarbon chain represented by (CH ₂ ) _t may be linear or branched, but is preferably linear.

Among these, R ² is a group represented by the above formula (3) or (6) from the process advantage that photoradical polymerization proceeds in a short time and the time required for the curing step can be shortened. It is preferable that

In said formula (1), R < ³ > shows any 1 type selected from the group which consists of a hydrogen atom, a C1-C6 alkyl group, a phenyl group, and an allyl group. When R ³ is an alkyl group, if the carbon number exceeds the above upper limit, the hydrocarbon chain length becomes too long, so that the resulting cured product may be decomposed or yellowed when exposed to ultraviolet rays for a long period of time. Tend to be. Among these, R ³ is more preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.

Furthermore, in said Formula (1), n, m, and j are following formula (i)-(iv):
n ≧ 2 (i),
m ≧ 1 (ii),
j ≧ 0 (iii),
n + m + j = h (iv)
[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]
An integer satisfying the condition represented by When the n in the formula (1) satisfies the condition represented by the formula (i), the cage silsesquioxane compound according to the present invention is a (meth) acryloyl group and a hydrocarbon having 4 to 10 carbon atoms. Since it has two or more reactive organic functional groups (groups represented by the formula (2)) containing a chain, the flexibility is sufficiently large and the radical polymerizability is excellent. Residual unreacted groups (residual double bonds) can be sufficiently reduced, and decomposition and yellowing when exposed to ultraviolet rays for a long time can be suppressed.

  In addition, when m in the formula (1) satisfies the condition represented by the formula (ii), a reactive functional group capable of forming a dense three-dimensional network structure with a short distance between crosslinks (the above-mentioned The group represented by any one of the formulas (3) to (6) can be imparted to the cage-type silsesquioxane compound, and therefore the rigidity and toughness excellent in the resin cured product obtained using the cage-type silsesquioxane compound. Can be given.

Furthermore, the cage silsesquioxane compound according to the present invention is almost completely obtained by satisfying all the conditions represented by the above formulas (i) to (iv) for n, m and j in the formula (1). In the curable resin composition obtained by using this, a further excellent moldability is achieved, and in the obtained resin cured product, further excellent transparency and low water absorption are achieved. And weather resistance are achieved. When n, m and j are each 2 or more, R ¹ , R ² and R ³ may be the same or different.

Examples of the cage silsesquioxane compound of the present invention include, in the general formula (1), R ² is a group represented by the formula (3), R ⁴ and R ⁵ are methyl groups, and n Is 2, m is 6, and j is 0.

[In formula (7), p shows the integer of 4-10, q shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (4), R ⁴ is a methyl group, n is 2, m is 6, j Is the following formula (8):

[In Formula (8), p shows the integer of 4-10, r shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (3), R ⁴ and R ⁵ are methyl groups, n is 4, and m is 4. Yes, j is 0:

[In formula (9), p shows the integer of 4-10, q shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (3), R ⁴ and R ⁵ are methyl groups, n is 3, and m is 7. Yes, the following formula (10) where j is 0:

[In formula (10), p shows the integer of 4-10, q shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (3), R ⁴ and R ⁵ are methyl groups, n is 5, and m is 5. Yes, j is 0:

[In formula (11), p represents an integer of 4 to 10, and q represents an integer of 1 to 3. ]
In the compound represented by formula (1), R ² is a group represented by formula (3), R ³ is an ethylene group (CH ₃ —CH ₂ —), R ⁴ and R ^5. Is a methyl group, n is 3, m is 5, and j is 2, the following formula (12):

[In formula (12), p shows the integer of 4-10, q shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (6), R ⁴ is a methyl group, n is 5, m is 5, j Is the following formula (13):

[In formula (13), p shows the integer of 4-10. ]
In the compound represented by formula (1), R ² is a group represented by formula (6), R ³ is an ethylene group (CH ₃ —CH ₂ —), and R ⁴ is a methyl group. And n is 5, m is 3, and j is 2, the following formula (14):

[In formula (14), p represents an integer of 4 to 10. ]
In the compound represented by formula (1), R ² is a group represented by formula (3), R ⁴ and R ⁵ are methyl groups, n is 4, and m is 8. Yes, j is 0:

[In formula (15), p shows the integer of 4-10, q shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (3), R ⁴ and R ⁵ are methyl groups, n is 7, and m is 5. Yes, j is 0:

[In formula (16), p shows the integer of 4-10, q shows the integer of 1-3. ]
In the compound represented by formula (1), R ² is a group represented by formula (6), R ⁴ is a methyl group, n is 10, m is 2, j Is the following formula (17):

[In formula (17), p shows the integer of 4-10. ]
In the compound represented by formula (1), R ² is a group represented by formula (6), R ³ is an ethylene group (CH ₃ —CH ₂ —), and R ⁴ is a methyl group. Where n is 4, m is 2 and j is 6:

[In formula (18), p shows the integer of 4-10. ]
The compound represented by these is more preferable.

As a method for producing such a cage silsesquioxane compound, for example, first, the following general formula (19):
R ¹ SiX ₃ (19)
[In Formula (19), R ¹ has the same meaning as R ¹ in Formula (1), and X is any one selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom, and a hydroxy group. Decomposable group is shown. ]
A silicon compound (A) represented by the following general formula (20):
R ² SiY ₃ (20)
[In Formula (20), R ² has the same meaning as R ² in Formula (1), and Y is any one selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom, and a hydroxy group. A hydrolyzable group is shown. ]
And, if necessary, the following general formula (21):
R ³ SiZ ₃ (21)
[In Formula (21), R ³ has the same meaning as R ³ in Formula (1), and Z is any one selected from the group consisting of an alkoxy group, an acetoxy group, a halogen atom, and a hydroxy group. The hydrolyzable group of is shown. ]
In the presence of a basic catalyst, the silicon compound (C) is mixed and subjected to hydrolysis reaction in water and partially condensed, and then the resulting hydrolysis reaction product is further mixed with a basic catalyst and a nonpolar solvent. And a method of recondensing in the presence of.

  Examples of the silicon compound (A) include 4-methacryloxybutyltrimethoxysilane, 4-methacryloxybutyltriethoxysilane, 5-methacryloxypentyltrimethoxysilane, 5-methacryloxypentyltriethoxysilane, and 6-methacryloxy. Hexyltrimethoxysilane, 6-methacryloxyhexyltriethoxysilane, 7-methacryloxyheptyltrimethoxysilane, 7-methacryloxyheptyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 8-methacryloxyoctyltriethoxysilane, 8-acryloxyoctyltrimethoxysilane, 8-acryloxyoctyltriethoxysilane, 9-methacryloxynonyltrimethoxysilane, 9-methacryloxynonyltriethoxysilane, 10- Takuri Loki Side Gilles trimethoxysilane, 10-methacryloxy-decyl triethoxysilane, and the like, may be used in combination of two or more even with these alone. Of these, 8-methacryloxyoctyltrimethoxysilane is preferably used from the viewpoint of easy availability of raw materials.

  Examples of the silicon compound (B) include methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of easy availability of raw materials, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxy It is preferable to use silane.

  Examples of the silicon compound (C) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltrimethoxysilane. Examples include ethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and the like. These may be used alone or in combination of two or more.

  As a mixing ratio of the silicon compound (A), the silicon compound (B), and the silicon compound (C), a molar ratio of the silicon compound (A) and the silicon compound (B) (number of moles of B: A Mole number) is 1: 4 to 13: 1, and the mole ratio of the silicon compound (C) to the sum of the silicon compound (A) and the silicon compound (B) (number of moles of A + B: number of moles of C). Is preferably mixed so as to be 1: 0 to 2: 5, and more preferably mixed so as to be 1: 0 to 2: 3.

  Examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl Examples thereof include ammonium hydroxide salts such as triethylammonium hydroxide. Among these, it is preferable to use tetramethylammonium hydroxide from the viewpoint of high catalytic activity in the hydrolysis reaction. The amount of such a basic catalyst is preferably 0.01 to 20% by mass with respect to the total mass of the silicon compounds (A) to (C). The basic catalyst is usually used as an aqueous solution.

  In the hydrolysis reaction, the presence of water is essential, but this can be supplied from an aqueous solution of the basic catalyst or added separately as water. The amount of water should just be more than the mass sufficient to hydrolyze a hydrolyzable group, and is the theoretical amount (mass) of the hydrolyzable group calculated from the mass of the silicon compounds (A) to (C). The amount is preferably 1.0 to 1.5 times.

  In the hydrolysis reaction, it is preferable to use a nonpolar solvent and / or a polar solvent. As such a solvent, if only a nonpolar solvent is used, the reaction system will not be uniform, and the hydrolysis reaction will not proceed sufficiently, and unreacted hydrolyzable groups tend to remain. It is preferable to use both a polar solvent and a polar solvent, or use only a polar solvent. As the polar solvent, alcohols such as methanol, ethanol and 2-propanol, or other polar solvents can be used. Among these, it is preferable to use lower alcohols having 1 to 6 carbon atoms that are soluble in water, and it is more preferable to use 2-propanol. The amount of the nonpolar solvent and / or the polar solvent used is preferably in a range where the total molar concentration (mol / liter: M) of the silicon compounds (A) to (C) is 0.01 to 10M. .

  As reaction conditions for the hydrolysis, the reaction temperature is preferably 0 to 60 ° C, and more preferably 20 to 40 ° C. When the reaction temperature is less than the lower limit, the reaction rate becomes slow, so that the hydrolyzable group remains in an unreacted state, and the reaction time tends to be long. On the other hand, when the reaction temperature exceeds the above upper limit, the reaction rate is too high, so that a complex condensation reaction proceeds, and as a result, high molecular weight of the hydrolysis reaction product tends to be promoted. Moreover, as reaction conditions for the hydrolysis, the reaction time is preferably 2 hours or more. When the reaction time is less than the lower limit, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group tends to remain in an unreacted state.

  As a method for recovering the hydrolysis reaction product after completion of the hydrolysis reaction, first, a method in which the reaction solution is made neutral or acidic using a weakly acidic solution, and then water or a water-containing reaction solvent is separated. It is done. Examples of the weakly acidic solution include sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, phosphoric acid solution, oxalic acid solution and the like. In addition, as a method of separating the water or the water-containing reaction solvent, the reaction solution is washed with a saline solution or the like to sufficiently remove moisture and other impurities, and then dried with a drying agent such as anhydrous magnesium sulfate. Means can be employed.

  In addition, as a method for recovering the hydrolysis reaction product when a polar solvent is used as the solvent, first, the polar solvent is removed by evaporation under reduced pressure, and then a nonpolar solvent is added to the hydrolysis reaction product. A method of washing and drying in the same manner as described above can be employed after dissolving the above. In addition, when a nonpolar solvent is used as the solvent, the hydrolysis reaction product can be recovered by separating the nonpolar solvent by means such as evaporation. However, the nonpolar solvent is used in the next recondensation reaction. If it can be used as the nonpolar solvent to be used, it is not necessary to separate it.

  In the hydrolysis reaction, since a condensation reaction of the hydrolyzate occurs together with the hydrolysis, most of the hydrolyzable groups in the silicon compounds (A) to (C) in the hydrolysis reaction, preferably almost all, are OH. Further, most of the OH group, preferably 80% or more, is condensed by the condensation reaction. Therefore, the hydrolysis reaction product contains a polycondensate produced by the condensation. Such a polycondensate varies depending on the reaction conditions, but has a number average molecular weight of 500 to 10,000. (Or oligomer) is a mixture of siloxanes having a plurality of types of cages, incomplete cages, ladders (ladders), and random structures. A cage-type silsesquioxane compound is included.

  In the method for producing a cage silsesquioxane compound of the present invention, the hydrolysis reaction product is further heated in the presence of a nonpolar solvent and a basic catalyst to condense the siloxane bond (referred to as recondensation). It is preferable to selectively produce a recondensate (a siloxane having a cage structure).

  The nonpolar solvent may be any solvent that is not or hardly soluble in water, but is preferably a hydrocarbon solvent. Examples of the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, xylene, etc. Among them, it is preferable to use toluene. The amount of the nonpolar solvent used may be an amount sufficient to dissolve the hydrolysis reaction product, and is 0.1 to 20 times the mass of the total mass of the hydrolysis reaction product. preferable.

  As the basic catalyst, a basic catalyst used in the hydrolysis reaction can be used, and among them, a catalyst soluble in a nonpolar solvent such as tetraalkylammonium is preferable. The amount of such a basic catalyst is preferably 0.01 to 20% by mass of the hydrolysis reaction product.

  As reaction conditions for the recondensation reaction, the reaction temperature is preferably 90 to 200 ° C, more preferably 100 to 140 ° C. When the reaction temperature is lower than the lower limit, a sufficient driving force is not obtained to cause the recondensation reaction, and the reaction tends not to proceed. On the other hand, when the reaction temperature exceeds the above upper limit, a reactive organic functional group such as a vinyl group or a (meth) acryloyl group may cause a self-polymerization reaction. Etc. tend to arise. Moreover, as reaction conditions of the said recondensation reaction, it is preferable that reaction time is 2 to 12 hours.

  Further, as the hydrolysis reaction product used for recondensation, it is preferable to use a product obtained by washing, drying and further concentrating as described above, but it can be used even if these treatments are not performed. Furthermore, in such a recondensation reaction, water may be present, but it is not necessary to add it positively, and it is preferable to keep it to the level of water supplied from the basic catalyst solution. However, when the hydrolysis is not sufficiently performed, it is preferable to add more water than is necessary for hydrolyzing the remaining hydrolyzable groups.

  In the method for producing a cage silsesquioxane compound of the present invention, the reaction solution after the recondensation reaction is washed to remove the catalyst, and the recondensation product obtained by concentrating with a rotary evaporator or the like, The cage-type silsesquioxane according to the present invention represented by the above formula (1) (preferably the formulas (7) to (18)) depending on the type of functional group, the reaction conditions and the state of the hydrolysis reaction product. A mixture of compounds is obtained. As long as the cage silsesquioxane compound according to the present invention is contained in the reaction product in an amount of 40% by mass or more, even if the reaction product is blended in the curable resin composition described later as it is, The effect of the cage silsesquioxane compound can be obtained.

  Next, the curable resin composition of the present invention will be described. The curable resin composition of the present invention contains the cage silsesquioxane compound of the present invention and a radical polymerization initiator, and the content of the cage silsesquioxane compound is 10 to 80% by mass. It is characterized by being.

  In the curable resin composition of the present invention, the cage silsesquioxane compound may be contained singly or in combination of two or more, and the reaction product may be You may use as it is. As content of the said cage silsesquioxane compound, the total mass of the said cage silsesquioxane compound needs to be 10-80 mass% with respect to the curable resin composition whole quantity of this invention. . When the content of the cage silsesquioxane compound is less than the lower limit, the physical properties such as the compatibility of the curable resin composition, the transparency of the obtained resin cured product, and the low water absorption are deteriorated. On the other hand, when the said upper limit is exceeded, the viscosity of curable resin composition will increase and manufacture of a molded article will become difficult. Further, from the viewpoint of better transparency and low water absorption, the content of the cage silsesquioxane compound is particularly preferably 15 to 80% by mass. In the present invention, when the curable resin composition contains a volatile solvent, the content of each component such as the cage silsesquioxane compound in the curable resin composition is the volatile content. It means the content relative to the mass of the curable resin composition excluding the mass of the curable solvent.

As the curable resin composition of the present invention, the ratio between the number of the number of R ² in R ¹ is a reactive functional group of the general formula (1) in the entire cage silsesquioxane compound (R ² : R ¹ ) is preferably 1: 6 to 13: 1. When the content of R ¹ is less than the above lower limit, the flexibility of the cage silsesquioxane compound tends to be lowered and radical polymerizability tends to be lowered. Since it becomes a cage-type silsesquioxane compound having a large chain content, the polarity tends to decrease and the compatibility with other resins tends to decrease. Moreover, from the viewpoint that the moldability of the resin composition and the transparency, low water absorption, and weather resistance of the resulting cured resin product become better, the ratio (R ² : R ¹ ) is from 1: 4 to More preferably, it is 13: 1.

  Examples of the radical polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. In the curable resin composition of the present invention, radical polymerization of the cage silsesquioxane compound is promoted by the radical polymerization initiator, and a cured resin having excellent strength and rigidity can be obtained.

  The thermal polymerization initiator is used when the curable resin composition of the present invention is thermally cured. Such a thermal polymerization initiator is preferably an organic peroxide, and examples of the organic peroxide include ketone peroxides, diacylalkyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, Examples thereof include alkyl peresters and percarbonates. Among these, dialkyl peroxide is preferable from the viewpoint of high catalytic activity. Specific examples of the dialkyl peroxide include cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di- Examples thereof include t-butyl peroxide, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate and the like. As the thermal polymerization initiator, one of these may be used alone, or two or more may be used in combination.

  The photopolymerization initiator is used when the curable resin composition of the present invention is photocured. As such a photopolymerization initiator, it is preferable to use compounds such as acetophenones, benzoins, benzophenones, thioxanthones, and acylphosphine oxides. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. It is done. As the photopolymerization initiator, one of these may be used alone, or two or more may be used in combination.

  As the radical polymerization initiator according to the present invention, the thermal polymerization initiator or the photopolymerization initiator may be used alone, or both may be used in combination. As content of such a radical polymerization initiator, it is preferable that it is 0.01-10 mass% in the curable resin composition of this invention, and it is more preferable that it is 0.05-5 mass%. If the content is less than the lower limit, the strength and rigidity of the resulting cured product (molded product) tends to be low because the composition is insufficiently cured. There is a tendency that a problem occurs that the molded body is colored.

  The curable resin composition of the present invention preferably further contains an unsaturated compound having a (meth) acryloyl group other than the cage-type silsesquioxane compound, ladder-type siloxane, and random-type siloxane. By containing such an unsaturated compound, it is possible to adjust the physical properties such as the viscosity of the curable resin composition and the rigidity and strength of the obtained cured resin product within a desired range.

  The unsaturated compound having a (meth) acryloyl group (hereinafter sometimes simply referred to as an unsaturated compound) is a compound other than the cage-type silsesquioxane compound, ladder-type siloxane and random-type siloxane of the present invention. The cage-type silsesquioxane compound of the present invention is not particularly limited as long as it has a (meth) acryloyl group that can be radically copolymerized, but when the viscosity of the curable resin composition is increased, From the viewpoint that production tends to be difficult, a reactive oligomer, a low-molecular-weight and / or low-viscosity reactive monomer, or the like, which is a polymer having about 20 to 20 repeating structural units, is preferable.

Examples of the reactive oligomer include epoxy acrylate, epoxidized acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, and polystyrylethyl methacrylate. Examples of the reactive monomer include butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate. Monofunctional monomers such as dicyclopentanyl diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol acrylate, dimethylol tricyclodecane diacrylate, bisphenol A diglycidyl ether di Acrylate, tetraethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylo Le propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, include polyfunctional monomers such as dipentaerythritol hexaacrylate. As the unsaturated compound, one of these may be used alone, or two or more may be used in combination.
When the curable resin composition of the present invention contains such an unsaturated compound, the content thereof may be a mass ratio to the cage silsesquioxane compound of the present invention (cage silsesquioxane compound: It is preferable that the saturated compound) has a mass of 10:90 to 80:20. When the content is less than the lower limit, the viscosity of the curable resin composition tends to increase and the moldability tends to decrease. On the other hand, when the content exceeds the upper limit, the compatibility of the curable resin composition and , Physical properties such as transparency, low thermal expansion, and low water absorption in the obtained cured resin tend to be lowered.

  Further, the curable resin composition of the present invention may further contain ladder-type siloxane and / or random-type siloxane within a range that does not impair the effects of the present invention. What was produced | generated as a by-product in manufacture of silsesquioxane resin is mentioned.

When the curable resin composition of the present invention contains such a ladder type siloxane and a random type siloxane, the content is the sum of the contents (mass) of the cage silsesquioxane compound of the present invention. When the content (mass) of the unsaturated compound is b, and the content (mass) of the ladder-type siloxane and random siloxane is c, the following formula:
10/90 ≦ a / (b + c) ≦ 80/20
It is preferable to satisfy the condition represented by the following formula:
20/80 ≦ a / (b + c) ≦ 75/25
It is more preferable that the condition represented by When the content of the cage silsesquioxane compound is less than the lower limit, the compatibility of the curable resin composition and the physical properties such as transparency, low thermal expansion, and low water absorption of the resulting cured resin product Tend to decrease. On the other hand, when exceeding the said upper limit, it exists in the tendency for the viscosity of a curable resin composition to increase and for a moldability to fall. Therefore, when using the reaction product of the aforementioned cage silsesquioxane as it is in the curable resin composition of the present invention, it is preferable to use a product subjected to purification treatment as necessary so as to satisfy the above conditions. .

  In addition, as the curable resin composition of the present invention, thermal polymerization is promoted for the purpose of improving the physical properties of the cured resin and / or promoting radical polymerization within the range that does not impair the effects of the present invention. An agent, a photoinitiator aid, a sharpening agent, and the like may further be contained. The curable resin composition of the present invention includes organic / inorganic fillers, inorganic fillers, plasticizers, flame retardants, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, Various additives such as a release agent, a foaming agent, a colorant, a crosslinking agent, a dispersion aid, and a resin component may further be contained.

In addition, the curable resin composition of the present invention is cast so as to have a thickness of 0.2 mm, and is irradiated with light with an integrated exposure of 2000 mJ / cm ² at room temperature using a high-pressure mercury lamp with an illuminance of 30 W / cm. When radical polymerization is performed, the reaction rate of the (meth) acryloyl group measured by infrared spectroscopy is preferably 70% or more, and more preferably 85% or more. The reaction rate of the (meth) acryloyl group is as described above.

  Although the conventional curable resin composition can improve the reaction rate of the (meth) acryloyl group by containing the unsaturated compound, the content of the (meth) acryloyl group increases. As a result, the water absorption of the resulting cured resin is increased and the water absorption resistance is deteriorated. Moreover, the weather resistance with respect to the ultraviolet-ray etc. of the resin cured material obtained will increase when content of the said unsaturated compound increases. On the other hand, since the curable resin composition of the present invention contains the cage silsesquioxane compound of the present invention, even if it does not contain the unsaturated compound, a (meth) acryloyl group. The reaction rate is sufficiently high in this way, the residual amount of unreacted groups in the resulting cured resin can be sufficiently reduced, and a cured resin having both excellent weather resistance and low water absorption can be obtained. Is possible.

  Next, the cured resin product of the present invention will be described. The cured resin of the present invention is obtained by radical polymerization of the curable resin composition of the present invention. Examples of the radical polymerization method include a method of thermosetting by heating and a method of photocuring by light irradiation. In the present invention, any one of the thermosetting and photocuring methods may be used alone, or both methods may be used in combination.

  As the conditions for the thermosetting, the reaction temperature is about room temperature (25 ° C.) to about 200 ° C. and the reaction time is 0.5 by appropriately selecting the thermal polymerization initiator and, if necessary, a thermal polymerization accelerator. It can be selected from a wide range of about 10 hours. Moreover, in this invention, it can be set as the molded object of a desired shape by polymerizing and hardening the said curable resin composition in a metal mold | die or on a steel belt. As a method for obtaining such a molded body, all of general molding methods such as injection molding, extrusion molding, compression molding, transfer molding, calendar molding, and cast (casting) molding can be applied.

  Examples of the photocuring method include a method of irradiating the curable resin composition with ultraviolet rays having a wavelength of 10 to 400 nm or visible rays having a wavelength of 400 to 700 nm for about 1 to 1200 seconds. The wavelength is not particularly limited, but is preferably near ultraviolet light having a wavelength of 200 to 400 nm. Examples of the lamp used as the ultraviolet ray generation source include a low pressure mercury lamp (output: 0.4 to 4 W / cm), a high pressure mercury lamp (40 to 160 W / cm), and an ultrahigh pressure mercury lamp (173 to 435 W / cm). ), Metal halide lamps (80 to 160 W / cm), and the like, and can be appropriately selected depending on the types of the photopolymerization initiator, the photoinitiator auxiliary, and the sharpening agent to be used. In the present invention, for example, the curable resin composition is injected into a mold made of a transparent material such as quartz glass, cured by radical polymerization, and then removed from the mold to form a desired shape. A molded body having a desired shape can be obtained by a method of manufacturing a body, a method of curing on a steel belt, or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In each synthesis example, GPC and mass spectrometry were performed by the methods shown below.

(GPC (gel permeation chromatography))
Using gel permeation chromatography (GPC) (device name: HLC-8320GPC (manufactured by Tosoh Corporation), solvent: THF, column: ultra high-speed semi-micro SEC column SuperH series, temperature: 40 ° C., speed: 0.6 ml / min) went. The number average molecular weight (Mn) and molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) were determined as converted values using standard polystyrene (trade name: TSK-GEL, manufactured by Tosoh Corporation).

(Mass spectrometry)
Electrospray ionization mass spectrometry (ESI-MS) apparatus (device name: LC apparatus; Separation module 2690 (manufactured by Waters), MS apparatus; ZMD4000 (manufactured by Micromass), measurement conditions: electrospray ionization method, capillary voltage: 3. 5 kV, cone voltage: +30 V).

(Synthesis Example 1)
First, in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 120 ml of 2-propanol (IPA) as a solvent, 150 ml of toluene, and 30.0 ml of a 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. I put it in. Subsequently, 8-methacryloxyoctyltrimethoxysilane (KBM-5803, manufactured by Shin-Etsu Chemical Co., Ltd.) 66.87 g (0.21 mol) and 3-methacryloxypropyltrimethoxysilane (SZ-6300, Toray Dow Corning Silicone) 52.15 g (0.21 mol) (mixed) was mixed and placed in the dropping funnel, and dropped into the reaction vessel at room temperature (about 25 ° C.) over 30 minutes with stirring. After completion of dropping, the mixture was stirred for 2 hours without heating. The solution (reaction solution) in the reaction vessel after stirring is adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water is added to separate the organic phase and the aqueous phase, and anhydrous magnesium sulfate is added to the organic phase. 10.0 g was added and dehydrated. The anhydrous magnesium sulfate was filtered off and concentrated by a rotary evaporator to obtain 81.03 g of a hydrolysis reaction product (silsesquioxane). This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents.

  Next, 45.0 g of the hydrolysis reaction product obtained above, 270 ml of toluene, and 6.5 ml of 10% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, Dean Stark, and a cooling tube. Water was distilled off. Further, the mixture was heated to 130 ° C. to carry out a recondensation reaction at the reflux temperature of toluene. The temperature at this time was 106 ° C. After refluxing toluene, the reaction was terminated after stirring for 2 hours. The solution (reaction solution) in the reaction vessel after stirring is adjusted to neutral (pH 7) with a citric acid aqueous solution, and then pure water is added to separate the organic phase and the aqueous phase, and anhydrous magnesium sulfate is added to the organic phase. 10.0 g was added and dehydrated. The anhydrous magnesium sulfate was filtered off and concentrated by a rotary evaporator to obtain 69.68 g of resin mixture 1. The obtained resin mixture 1 was a colorless viscous liquid soluble in various organic solvents.

The graph which shows the result of GPC and the mass spectrometry of the obtained resin mixture 1 is shown in FIG.1 and FIG.2, respectively. In the result (chromatogram) of GPC, peak 1 (Mw = 4,501, Mw) including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (n + m) in general formula (1) is greater than 14. /Mn=1.06) and peak 2 (Mw = 2,012, Mw / Mn = 1.03) containing a cage-type silsesquioxane resin in which (n + m) is 14 or less, From the results and the results of mass spectrometry, the obtained resin mixture 1 is represented by the following formula (I):
[CH ₂ = C (CH ₃ ) COOC ₈ H ₁₆ SiO _3/2 ] _n [CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m (I)
It was confirmed that it is a resin mixture containing the cage-type silsesquioxane resin represented by. In addition, in the obtained resin mixture 1, content of the cage silsesquioxane resin represented by the formula (I) was 81% by mass.

(Synthesis Example 2)
70 ml of 2-propanol (IPA), 170 ml of toluene, 92.7 g (0.29 mol) of 8-methacryloxyoctyltrimethoxysilane, and 24.1 g (0.097 mol) of 3-methacryloxypropyltrimethoxysilane. Except for this, 82.30 g of a hydrolysis reaction product (silsesquioxane) was obtained in the same manner as in Synthesis Example 1. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, 36.55 g of a resin mixture 2 was obtained in the same manner as in Synthesis Example 1 except that 40.0 g of this hydrolysis reaction product was used and 130 ml of toluene was used. The obtained resin mixture 2 was a colorless viscous liquid soluble in various organic solvents.

  A graph (chromatogram) showing the GPC result of the obtained resin mixture 2 is shown in FIG. In the chromatogram, the peak 1 (Mw = 4,460, Mw / Mn = 1...) Including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (n + m) in the general formula (1) is greater than 14. 03) and peak 2 (Mw = 2,140, Mw / Mn = 1.03) containing a cage-type silsesquioxane resin in which the above (n + m) is 14 or less were detected. From the results, it was confirmed that the obtained resin mixture 2 was a resin mixture containing a cage silsesquioxane resin represented by the above formula (I). In addition, in the obtained resin mixture 2, content of the cage silsesquioxane resin represented by the formula (I) was 83% by mass.

(Synthesis Example 3)
Synthesis except that 90 ml of 2-propanol (IPA), 28.32 g (0.089 mol) of 8-methacryloxyoctyltrimethoxysilane, and 66.26 g (0.27 mol) of 3-methacryloxypropyltrimethoxysilane were used. In the same manner as in Example 1, 62.30 g of a hydrolysis reaction product (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, 34.80 g of a resin mixture 3 was obtained in the same manner as in Synthesis Example 1 except that 43.0 g of this hydrolysis reaction product was used. The obtained resin mixture 3 was a colorless viscous liquid soluble in various organic solvents.

  The graph (chromatogram) which shows the result of GPC of the obtained resin mixture 3 is shown in FIG. In the chromatogram, the peak 1 (Mw = 4,012, Mw / Mn = 1.M) including the cage silsesquioxane resin, the ladder type siloxane, and the random type siloxane in which (n + m) in the general formula (1) is greater than 14. 10) and peak 2 (Mw = 1,640, Mw / Mn = 1.41) containing a cage-type silsesquioxane resin in which (n + m) is 14 or less, and the results and mass spectrometry From the results, it was confirmed that the obtained resin mixture 3 was a resin mixture containing a cage silsesquioxane resin represented by the above formula (I). In addition, in the obtained resin mixture 3, content of the cage silsesquioxane resin represented by the formula (I) was 68% by mass.

(Synthesis Example 4)
60 ml of 2-propanol (IPA), 100 ml of toluene, 87.25 g (0.27 mol) of 8-methacryloxyoctyltrimethoxysilane, and vinyltrimethoxysilane (KBM-) instead of 3-methacryloxypropyltrimethoxysilane 1003, manufactured by Shin-Etsu Chemical Co., Ltd.) 65.94 g of a hydrolysis reaction product (silsesquioxane) was obtained in the same manner as in Synthesis Example 1 except that 40.61 g (0.27 mol) was used. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, using this hydrolysis reaction product, 38.20 g of a resin mixture 4 was obtained in the same manner as in Synthesis Example 1 except that the reflux temperature of toluene was 105 ° C. The obtained resin mixture 4 was a colorless viscous liquid soluble in various organic solvents.

The graph (chromatogram) which shows the result of GPC of the obtained resin mixture 4 is shown in FIG. In the chromatogram, the peak 1 (Mw = 3,528, Mw / Mn = 1.M) including the cage silsesquioxane resin, the ladder type siloxane, and the random type siloxane in which (n + m) in the general formula (1) is greater than 14. 21) and peak 2 (Mw = 1,306, Mw / Mn = 1.03) containing a cage-type silsesquioxane resin in which (n + m) is 14 or less, and this result and mass spectrometry From the results, the obtained resin mixture 4 is represented by the following formula (II):
[CH ₂ = C (CH 3) COOC ₈ H ₁₆ SiO _3/2 ] _n [CH ₂ = CHSiO _3/2 ] _m (II)
It was confirmed that it is a resin mixture containing the cage-type silsesquioxane resin represented by. In addition, in the obtained resin mixture 4, content of the cage silsesquioxane resin represented by the formula (II) was 75 mass%.

(Synthesis Example 5)
100 ml of 2-propanol (IPA) and 240 ml of toluene, 38.16 g (0.12 mol) of 8-methacryloxyoctyltrimethoxysilane, and 9.92 g (0.04 mol) of 3-methacryloxypropyltrimethoxysilane Furthermore, the hydrolysis reaction product was the same as in Synthesis Example 1 except that 24.00 g (0.16 mol) of ethyltrimethoxysilane (LS-890, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and placed in the dropping funnel. 45.20 g of (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, 36.05 g of a resin mixture 5 was obtained in the same manner as in Synthesis Example I except that 40.0 g of this hydrolysis reaction product was used and the reflux temperature of toluene was 108 ° C. The obtained resin mixture 5 was a colorless viscous liquid soluble in various organic solvents.

About the obtained resin mixture 5, the graph (chromatogram) which shows the result of GPC is shown in FIG. In the chromatogram, the peak 1 (Mw = 3, 652, Mw / Mn = 1...) Including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (n + m + j) in the general formula (1) is greater than 14. 21) and peak 2 (Mw = 1,295, Mw / Mn = 1.03) containing a cage silsesquioxane resin in which (n + m + j) is 14 or less, and the results and mass spectrometry From the results, the obtained resin mixture 5 is represented by the following formula (III):
[CH ₂ = C (CH ₃ ) COOC ₈ H ₁₆ SiO _3/2 ] _n [CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m [CH ₃ CH ₂ SiO _3/2 ] _j. .. (III)
It was confirmed that it is a resin mixture containing the cage-type silsesquioxane resin represented by. In addition, in the obtained resin mixture 5, content of the cage silsesquioxane resin represented by the formula (III) was 43% by mass.

(Synthesis Example 6)
Synthesis Example I except that 60 ml of 2-propanol (IPA), 120 ml of toluene, 69.27 g (0.28 mol) of 3-methacryloxypropyltrimethoxysilane were used, and 8-methacryloxyoctyltrimethoxysilane was not used. In the same manner as above, 48.36 g of a hydrolysis reaction product (silsesquioxane) was obtained. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, 41.40 g of a resin mixture 6 was obtained in the same manner as in Synthesis Example 1 except that the hydrolysis reaction product was used and 260 ml of toluene was used. The obtained resin mixture 6 was a colorless viscous liquid soluble in various organic solvents.

About the obtained resin mixture 6, the graph (chromatogram) which shows the result of GPC is shown in FIG. In the chromatogram, peak 1 (Mw = 1,769, Mw / Mn = 1.08) containing all methacryloxypropyl cage silsesquioxane resin was detected, and it was obtained from this result and the result of mass spectrometry. The resin mixture 6 has the following formula (IV):
[CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _m (IV)
It was confirmed that this is a resin mixture containing a cage silsesquioxane resin in which m is 10. In addition, in the obtained resin mixture 6, content of the cage silsesquioxane resin represented by the formula (IV) was 84% by mass.

(Synthesis Example 7)
80 ml of 2-propanol (IPA), 160 ml of toluene, 48.06 g (0.19 mol) of 3-methacryloxypropyltrimethoxysilane, and 28.68 g of vinyltrimethoxysilane instead of 8-methacryloxyoctyltrimethoxysilane 48.68 g of a hydrolysis reaction product (silsesquioxane) was obtained in the same manner as in Synthesis Example I except that (0.19 mol) was used, and this hydrolysis reaction product was used as a resin mixture 7.

About the obtained resin mixture 7, the graph (chromatogram) which shows the result of GPC is shown in FIG. In the chromatogram, peak 1 (Mw = 6,047, Mw) including a cage-type silsesquioxane resin, ladder-type siloxane, and random-type siloxane in which (m ′ + m ″) in the following general formula (V) is greater than 14. /Mn=1.05) and peak 2 (Mw = 1,891, Mw / Mn = 1.41) containing a cage-type silsesquioxane resin in which (m ′ + m ″) is 14 or less. From this result and the result of mass spectrometry, the obtained resin mixture 7 is represented by the following formula (V):
[CH ₂ = C (CH ₃ ) COOC ₃ H ₆ SiO _3/2 ] _{m ′} [CH ₂ = CHSiO _3/2 ] _{m ″} (V)
It was confirmed that it is a resin mixture containing the cage-type silsesquioxane resin represented by. In addition, in the obtained resin mixture 7, content of the cage silsesquioxane resin represented by the formula (V) was 40% by mass.

(Synthesis Example 8)
130 ml of 2-propanol (IPA) and 260 ml of toluene, and without using 8-methacryloxyoctyltrimethoxysilane, instead of 3-methacryloxypropyltrimethoxysilane, 93.65 g (0.632 mol) of vinyltrimethoxysilane was used. 44.03 g of a hydrolysis reaction product (silsesquioxane) was obtained in the same manner as in Synthesis Example I except that it was used. This hydrolysis reaction product was a colorless viscous liquid soluble in various organic solvents. Next, 38.24 g of a resin mixture 8 was obtained in the same manner as in Synthesis Example 1 except that 42.0 g of this hydrolysis reaction product was used and toluene was changed to 260 ml. The obtained resin mixture 8 was a colorless viscous liquid soluble in various organic solvents.

About the obtained resin mixture 8, the graph (chromatogram) which shows the result of GPC is shown in FIG. In the chromatogram, peak 1 (Mw = 3,229, n) in general formula (1), which includes all vinyl cage silsesquioxane resins, ladder-type siloxanes, and random-type siloxanes in which n is 0 and m is greater than 14. Mw / Mn = 1.40) and peak 2 (Mw = 797, Mw / Mn = 1.41) including an all-vinyl cage silsesquioxane resin in which m is 14 or less. And from the results of mass spectrometry, the obtained resin mixture 8 is represented by the following formula (VI):
[CH ₂ = CHSiO _3/2 ] _m (VI)
It was confirmed that it is a resin mixture containing the cage-type silsesquioxane resin represented by. In addition, in the obtained resin mixture 8, content of the cage silsesquioxane resin represented by the formula (VI) was 83% by mass.

Example 1
First, 1-hydroxycyclohexyl phenyl ketone (Irg184, manufactured by Ciba Japan Co., Ltd.) is used as a polymerization initiator with respect to 100 parts by mass of the resin mixture 1 containing the cage silsesquioxane compound obtained in Synthesis Example 1. 5 parts by mass was mixed to obtain a curable resin composition. Next, 2 g of the obtained curable resin composition was applied on a glass plate, a metal spacer having a height of 0.2 mm was disposed, and the glass plate was further covered from above, and the resin composition was allowed to flow by its own weight. After extending to a thickness of 0.2 mm, a 30 W / cm high-pressure mercury lamp was used and cured with an integrated exposure amount of 2000 mJ / cm ² to obtain a film-like resin cured product.

(Example 2)
First, 70 parts by mass of the resin mixture 1 containing the cage silsesquioxane compound obtained in Synthesis Example 1 and 30 parts by mass of dicyclopentanyl diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) This was mixed, and 1.5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (Irg184, manufactured by Ciba Japan Co., Ltd.) and 1.0 part by mass of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) as a polymerization initiator. Were mixed to obtain a curable resin composition. Next, a film-like cured resin was obtained in the same manner as in Example 1 except that the obtained curable resin composition was used.

(Example 3)
A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 2 obtained in Synthesis Example 2 was used in place of the resin mixture 1.

Example 4
A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 2 obtained in Synthesis Example 2 was used in place of the resin mixture 1.

(Example 5)
A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 3 obtained in Synthesis Example 3 was used in place of the resin mixture 1.

(Example 6)
A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 3 obtained in Synthesis Example 3 was used in place of the resin mixture 1.

(Example 7)
The same procedure as in Example 1 was performed except that 1.0 mass part of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) was further mixed using the resin mixture 4 obtained in Synthesis Example 4 instead of the resin mixture 1. Thus, a curable resin composition was obtained. Next, using the obtained curable resin composition, after curing using a high-pressure mercury lamp, the cured resin was obtained in the same manner as in Example 1 except that it was further heated at 200 ° C. for 1 hour in a nitrogen atmosphere. Obtained.

(Example 8)
A curable resin composition was obtained in the same manner as in Example 2 except that the resin mixture 4 obtained in Synthesis Example 4 was used in place of the resin mixture 1. Next, using the obtained curable resin composition, after curing using a high-pressure mercury lamp, the cured resin was obtained in the same manner as in Example 2 except that it was heated at 200 ° C. for 1 hour in a nitrogen atmosphere. Obtained.

Example 9
A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 5 obtained in Synthesis Example 5 was used in place of the resin mixture 1.

(Example 10)
A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 5 obtained in Synthesis Example 5 was used in place of the resin mixture 1.

(Comparative Example 1)
A curable resin composition and a cured resin were obtained in the same manner as in Example 1 except that the resin mixture 6 obtained in Synthesis Example 6 was used in place of the resin mixture 1.

(Comparative Example 2)
A curable resin composition and a cured resin were obtained in the same manner as in Example 2 except that the resin mixture 6 obtained in Synthesis Example 6 was used in place of the resin mixture 1.

(Comparative Example 3)
The same procedure as in Example 1 was performed except that 1.0 mass part of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) was further mixed using the resin mixture 7 obtained in Synthesis Example 7 instead of the resin mixture 1. Thus, a curable resin composition was obtained. Next, using the obtained curable resin composition, after curing using a high-pressure mercury lamp, the cured resin was obtained in the same manner as in Example 1 except that it was further heated at 200 ° C. for 1 hour in a nitrogen atmosphere. Obtained.

(Comparative Example 4)
A curable resin composition was obtained in the same manner as in Example 2 except that the resin mixture 7 obtained in Synthesis Example 7 was used in place of the resin mixture 1. Next, using the obtained curable resin composition, after curing using a high-pressure mercury lamp, the cured resin was obtained in the same manner as in Example 2 except that it was heated at 200 ° C. for 1 hour in a nitrogen atmosphere. Obtained.

(Comparative Example 5)
The same procedure as in Example 1 was performed except that 1.0 mass part of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) was further mixed using the resin mixture 8 obtained in Synthesis Example 8 instead of the resin mixture 1. Thus, a curable resin composition was obtained. Next, using the obtained curable resin composition, after curing using a high-pressure mercury lamp, the cured resin was obtained in the same manner as in Example 1 except that it was further heated at 200 ° C. for 1 hour in a nitrogen atmosphere. Obtained.

(Comparative Example 6)
A curable resin composition was obtained in the same manner as in Example 2 except that the resin mixture 8 obtained in Synthesis Example 8 was used in place of the resin mixture 1. Next, using the obtained curable resin composition, after curing using a high-pressure mercury lamp, the cured resin was obtained in the same manner as in Example 2 except that it was heated at 200 ° C. for 1 hour in a nitrogen atmosphere. Obtained.

  About the curable resin composition and resin hardened | cured material obtained in Examples 1-10 and Comparative Examples 1-6, the measurement of a reaction rate, the measurement of a water absorption, total light transmittance, and a weather resistance evaluation were performed with the following method. It was.

(Measurement of reaction rate)
First, about the curable resin composition obtained by each Example and the comparative example, the (meth) acryloyl group in 1728cm < ^-1 > was used using the microscopic infrared spectroscopy apparatus (brand name: FT-IR6100, JASCO Corporation make). Absorbance (AW _{C = O} ) derived from the stretching vibration of the carbon-oxygen double bond (C = O) therein, and the carbon-carbon double bond (C = C) in the (meth) acryloyl group at 1635 cm ^-1 The maximum absorbance (AW _{C = C} ) derived from the stretching vibration of _C ) was measured. Then, after the radical polymerization of the curable resin composition, the obtained cured resin in the Examples and Comparative Examples, the maximum absorbance at the maximum absorbance _{(AF C = O)} and 1635 cm ^-1 in 1728 cm ^-1 (AF _{C = C} ) was measured as above. The ratio of AW _{C = O} to AW _{C = C} (AW = AW _{C = O} / AW _{C = C} ) and the ratio of AF _{C = O} to AF _{C = C} (AF = AF _{C = O} / AF _{C = C} ) from the following formula:
Double bond change rate (A _R ) = (1−AW / AF) × 100
Thus, the double bond change rate (A _R (%)) of the (meth) acryloyl group was obtained, and this was defined as the reaction rate of the (meth) acryloyl group. The results are shown in Table 1.

(Measurement of water absorption)
First, the obtained cured resin was kept at 50 ° C. for 24 hours and pre-dried. Next, the water absorption rate was measured based on the plastic-water absorption rate calculation method (JISK7209). The obtained results are shown in Table 1.

(Measurement of total light transmittance)
About the obtained cured resin (thickness 0.2 mm), the transmitted light intensity and the incident light intensity were measured using NDH2000 (Nippon Denshoku Co., Ltd.), and the following formula:
Total light transmittance was calculated by total light transmittance (%) = transmitted light intensity / incident light intensity. The obtained results are shown in Table 1.

(Weather resistance evaluation)
The obtained cured resin (thickness: 0.2 mm) was irradiated with ultraviolet rays for 72 hours under the condition of a lamp distance of 5 cm using a QUV Accelerated Weathering Tester (use lamp “UVB-313”) manufactured by Q-Lab. did. For the cured resin before and after being exposed to ultraviolet rays, the yellowness (YI) was determined according to the plastic-yellowness and yellowness determination methods (JISK7373). The results are shown in Table 1.

  As is clear from the results shown in Table 1, the cured resin products obtained in Examples 1 to 10 have excellent transparency and low water absorption, and are sufficiently excellent in weather resistance. confirmed. Moreover, when the crack of the resin hardened | cured material obtained in Examples 1-10 was observed visually, a crack and a fracture | rupture were not observed in any hardened | cured material (film), The curable resin composition of this invention is It was confirmed to have excellent moldability. On the other hand, in Comparative Examples 1 to 6, although a cured product having a high transmittance was obtained to some extent, it was confirmed that all cured products had high yellowness and poor weather resistance after being exposed to ultraviolet rays. Furthermore, it was confirmed that the cured resin obtained in Comparative Examples 1 and 2 has a particularly high water absorption rate. In Comparative Example 5, the cured product was cracked, and a cured product specimen having a size that could be measured could not be obtained.

  As described above, according to the present invention, a curable resin composition having excellent moldability, and a cured resin having excellent transparency and low water absorption and excellent weather resistance are obtained. It is possible to provide a cage-type silsesquioxane compound that can be used, a curable resin composition using the same, and a cured resin obtained by curing the same.

  Such resin cured products include liquid crystal display element substrates, color filter substrates, organic EL display element substrates, electronic paper substrates, TFT substrates, solar cell substrates and other transparent substrates, touch panels, and transparent electrode films. As a glass substitute material for light guide plates, protective films, polarizing films, retardation films, optical films such as lens sheets, various transport machines, window materials for houses, etc., it has a wide range of applications and its industrial utility value It is extremely expensive.

Claims (6)

The following general formula (1):
[R ¹ SiO _3/2 ] _n [R ² SiO _3/2 ] _m [R ³ SiO _3/2 ] _j (1)
{In formula (1), R ¹ is the following general formula (2):
[In Formula (2), R ⁴ represents a hydrogen atom or a methyl group, and p represents an integer of 4 to 10. ]
R ² represents the following general formula (3):
[In Formula (3), R ⁵ represents a hydrogen atom or a methyl group, and q represents an integer of 1 to 3. ]
A group represented by the following general formula (4):
[In Formula (4), r shows the integer of 1-3. ]
A group represented by the following general formula (5):
[In Formula (5), s shows the integer of 1-3. ]
And a group represented by the following formula (6):
Any one group selected from the group consisting of the groups represented by: R ³ is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group and an allyl group; N, m and j are the following formulas (i) to (iv):
n ≧ 2 (i),
m ≧ 1 (ii),
j ≧ 0 (iii),
n + m + j = h (iv)
[In the formula (iv), h represents any integer selected from the group consisting of 8, 10, 12, and 14. ]
When n, m and j are each 2 or more, R ¹ , R ² and R ³ may be the same or different. }
A cage-type silsesquioxane compound represented by the formula:   Curing characterized in that it contains the cage silsesquioxane compound according to claim 1 and a radical polymerization initiator, and the content of the cage silsesquioxane compound is 10 to 80% by mass. Resin composition.   The curable resin composition according to claim 2, further comprising an unsaturated compound having a (meth) acryloyl group other than the cage-type silsesquioxane compound, ladder-type siloxane, and random-type siloxane. Measured by infrared spectroscopy when radical polymerization is performed at room temperature using a high-pressure mercury lamp with an illuminance of 30 W / cm and light irradiation with an integrated exposure of 2000 mJ / cm ² using a high-pressure mercury lamp with an illuminance of 30 W / cm. 4. The curable resin composition according to claim 2, wherein a reaction rate of the (meth) acryloyl group is 70% or more. 5.   Content of the said radical polymerization initiator is 0.01-10 mass%, The curable resin composition as described in any one of Claims 2-4 characterized by the above-mentioned. A cured resin , which is a radical polymer of the curable resin composition according to any one of claims 2 to 5.