JP3254018B2 - Polyorganosilsesquioxane and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyorganosilsesquioxane whose composition with a monomer or macromonomer having a polymerizable unsaturated bond in the molecule is useful as an antistatic agent for plastic products and the like, and its production. About the method.

[0002]

2. Description of the Related Art Plastic products are used in large quantities in various fields, but generally have good electrical insulation, so they are easily charged with static electricity, easily adhere to dust and dirt, and impair the beautiful appearance of the products. It is well known that the performance of electric insulation and the like is deteriorated, and this is a major obstacle depending on the purpose of use.

Conventionally, as an antistatic method for these plastic products, a surfactant is mainly applied to the product surface,
Alternatively, it is performed by kneading a surfactant into plastic. However, in the case of the coating type, since it is easily removed from the product surface during use, the effect is not persistent, and the surface is easily tacky and sticky.

[0004] On the other hand, in the case of the kneading type, there are major drawbacks such as decomposition or discoloration during thermoforming, and bleeding on the surface during use of the product. No satisfactory antistatic effect has been obtained.

On the other hand, recently, the surface of a molded product based on plastic products (resin such as polyvinyl chloride, polystyrene, polyurethane, polycarbonate, polybutadiene, ABS, acrylic resin, etc.) has a printed surface protection, abrasion resistance, and scratch resistance. In order to improve physical and chemical performance such as strength, a method of applying a UV-curable resin composition has begun to be used.

For example, JP-A-56-22306 discloses a composition having an antistatic effect comprising an acrylic UV-curable composition and polyethylene glycol diacrylate. However, this method exhibits excellent performance in a normal temperature and normal humidity atmosphere, but has a drawback that its performance is significantly deteriorated in a high temperature and high humidity atmosphere.

[0007]

SUMMARY OF THE INVENTION The present invention has been a problem in the prior art. However, in the antistatic method for plastic products, excellent durability, water resistance, transparency even at high temperature and high humidity can be obtained.
Development of a novel polymerizable polyorganosilsesquioxane useful as a main component of a resin composition capable of providing a glossy, high antistatic effect and high hardness coating film by a simple operation and a method for producing the same It is intended for.

[0008]

According to the present invention, there is provided a compound represented by the general formula (1): R ¹ —SiO _3/2 (1) wherein R ¹ is a quaternary ammonium type cationic group. A substituted hydrocarbon group having 1 to 12 carbon atoms as a group), a general formula (2): R ² —SiO _3/2 (2) (where R ² is an alkyl group having 1 to 3 carbon atoms), And a structural unit represented by the following general formula (3): R ³ —SiO _3/2 (3) (wherein R ³ is an organic residue containing a polymerizable unsaturated bond). : (3) molar ratio of 1 to 80: 5 to 90: 5 to 90 (provided that (1) + (2)
+ (3) = 100. Ladder type polyorganosilsesquioxane characterized by having a number average molecular weight of 600 to 100,000, a trialkoxysilane represented by the general formula (4), R ¹ —Si (OR ⁴ ) ₃ ... (4) Trialkoxysilane represented by general formula (5), R ² —Si (OR ⁵ ) ₃ ... (5) and trialkoxysilane represented by general formula (6) Alkoxysilane R ³ —Si (OR ⁶ ) ₃ (6) (wherein, R ^{1 to} R ³ are the same as above; R ^{4 to} R ⁶ are alkyl groups having 1 to 3 carbon atoms); The molar ratio of (4), (5) and (6) is from 1 to 80:
5 to 90: 5 to 90 , and (4), (5)
And a method for producing a ladder-type polyorganosilsesquioxane, characterized by co-condensing 1.5 times or more moles of water with respect to the total moles of (6) and an acid or base, and A part or all of the trialkoxysilane represented by the general formula (4) may be substituted by a general formula (7) R ⁷ —Si (OR ⁸ ) ₃ (7) (where R ⁷ is an amino group. R ⁸ is an alkyl group having 1 to 3 carbon atoms), and a copolycondensation is performed in place of the trialkoxysilane represented by the formula (1), and then the amino group in R ^{7 is} converted into a quaternary ammonium. The above problem has been solved by developing a method for producing an organosilsesquioxane.

Hereinafter, the present invention will be described in detail. In the polyorganosilsesquioxane of the present invention, in the structural unit represented by the general formula (1), R ¹ is a substituted hydrocarbon group having a quaternary ammonium salt type cation group as a substituent.

Examples of the quaternary ammonium salt type cationic group in R ¹ include-(NH ₃ ) ⁺ X ^- ,-[N (CH
_{3) 3]} ⁺ X ^-,

Embedded image _{- [NH 2 C 6 H 5} ] + X -, - [N (CH 3) 2 CH
_{2 CH 2 OCOC (CH 3)} = CH 2] + X -, - [N
_{(CH 3) 2 C 18 H} 37] + X -, - [N (C 2 H 5) 2
^{_{C 3 H 9] + X -}} ,

Embedded image _{- [NH-CH 2 -CH 2} -NH 2 -CH 2 -C 6 H
_5] ⁺ X ^- (where, ⁺ X ^- is an anionic atom or molecule.)
And so on.

Examples of the substituted hydrocarbon group in R ¹ include an alkylene group such as methylene, ethylene and trimethylene; or a substituted alkylene group having an alkyl group, alkenyl group, aryl group, cycloalkyl group or the like as a substituent; or These groups have a carbon atom of 1 in which some of the hydrogen atoms bonded to the carbon atoms are replaced by halogen atoms, cyano groups, etc.
To 12 and preferably 2 to 4 substituted hydrocarbon groups.

R ² in the structural unit represented by the general formula (2)
Is an alkyl group having 1 to 3 carbon atoms, and thus methyl,
Either an ethyl, propyl or isopropyl group.

R ^{3 in the} structural unit represented by the general formula (3) is a group containing a polymerizable unsaturated bond, and may be an organic residue having at least one polymerizable carbon-carbon double bond therein. Good.

As a specific example of the organic residue, CH ₂ ＣC
_{(R ') -, CH 2} = C (R') - COOR "-, C
H ₂ ＣＨCHCH ₂ OCOR ′ ″ OCOR ′ ″ − (where R ′ is hydrogen or a methyl group, R ″ and R ′ ″ are divalent hydrocarbon groups having 1 to 18 carbon atoms, for example, methylene, ethylene Propylene, butylene, hexylene, phenylene, cyclohexylene, etc.).

The molar ratios of the general formulas (1), (2) and (3) of the constituents in this polyorganosilsesquioxane are 1-80 as (1) :( 2) :( 3).
5 to 90: 5 to 90 (however, (1) + (2) + (3) =
Set to 100. ).

If the ratio is out of this range, the polymerizability decreases and a long curing time is required, or the gelation easily occurs, making it difficult to handle, or the coating film loses its durability. Further, the number average molecular weight of this polyorganosilsesquioxane is from 600 to 100,000, preferably from 800 to 30,000.

An example of the method for producing the polyorganosilsesquioxane in the present invention will be described below.

The polyorganosilsesquioxane of the present invention comprises a trialkoxysilane represented by the general formula (4), R ¹ -Si (OR ⁴ ) ₃ ... (4) Alkoxysilane and R ² —Si (OR ⁵ ) ₃ ... (5) trialkoxysilane R ³ —Si (OR ⁶ ) ₃ ... (6) represented by the general formula (6) (wherein R ¹ to R ³ are as described above .R ⁴ ~
R ⁶ is an alkyl group having 1 to 3 carbon atoms. ) May be mixed and co-condensed in a ratio that is a structural unit of the target polyorganosilsesquioxane ratio.

In the co-condensation, the reaction is carried out in the coexistence of water and an acid or a base in a molar amount of at least 1.5 times the total molar amount of the silane. It can be synthesized by removing it.

In the present invention, instead of the trialkoxysilane represented by the general formula (4), the general formula (7) R ⁷ —Si (OR ⁸ ) ₃ (7) (where R ⁷ is amino The above-mentioned co-condensation using a trialkoxysilane represented by a substituted hydrocarbon group having a group as a substituent and R ⁸ is an alkyl group having 1 to 3 carbon atoms, and then converting the amino group in R ⁷ to 4 Alternatively, the compound may be synthesized by converting the compound into a quaternary ammonium and then removing coexisting water, by-product alcohol, water and the like.

Specific examples of the trialkoxysilane having a quaternary ammonium group represented by the general formula (4) include the following. [H ₃ N—C ₃ H ₆ —Si (OCH ₃ ) ₃ ] ⁺ Cl ⁻ [H ₃ N—C ₃ H ₆ —Si (OC ₂ H ₅ ) ₃ ] ⁺ Cl ⁻ [H ₃ N—C ₃ H _{6 -Si (OC 3 H 7)} 3] + Cl - [(CH 3) 3 N-C 3 H 6 -Si (OCH 3) 3] +
Cl ^-

Embedded image _{[C 6 H 5 NH 2 C} 3 H 6 -Si (OCH 3) 3] + C
l ^- [(CH ₃ ) ₃ NC ₃ H ₆ -Si (OCH ₃ ) ₃ ] ⁺
CH ₃ OSO ₃ ^-

Embedded image And the like, but are not limited thereto.
One or a mixture of two or more of these compounds can be used.

Specific examples of the trialkoxysilane represented by the general formula (5) include the following.

Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriethoxysilane, propyltripropoxysilane,
Propyltriisopropoxysilane and the like can be mentioned, and these can be used as one kind or as a mixture of two or more kinds.

As a specific example of the trialkoxysilane having an unsaturated group represented by the general formula (6), CH ₂ ＣＨCH
Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OC ₂ H ₅ )
₃ , CH ₂ ＣＨCHSi (OC ₃ H ₇ ) ₃ , CH ₂ ＣＨCHC
H ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCH ₂ Si (O
C ₂ H ₅ ) ₃ , CH ₂ ＣＨCHCH ₂ Si (OC ₃ H ₇ )
₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OCH ₃ )
₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OC ₂ H
₅ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OC _{3
H 7) 3, CH 2 =} C (CH 3) -COO (CH 2) 3
_{Si (OCH 3) 3, CH} 2 = C (CH 3) -COO
(CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₂ ＣC (CH
₃ ) —COO (CH ₂ ) ₃ Si (OC ₃ H ₇ ) ₃ , CH
_{3 -CH = CHCOO (CH 2)} 3 Si (OCH 3)
_{3, CH 2 = CH-C} 6 H 4 CH 2 CH 2 Si (OCH
_{3) 3, CH 2 = CH-} (CH 2) 4 -Si (OCH
_{3) 3, CH 2 = CH-} (CH 2) 8 -Si (OCH
_{3) 3, CH 2 = CH} -O- (CH 2) 3 -Si (OC
H ₃ ) ₃ , CH ₂ ＣＨCHOCO (CH ₂ ) ₁₀ Si (OC
_{H 3) 3, CH 2 =} C (CH 3) -COO (CH 2) 2 O
(CH ₂ ) ₃ —Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCH ₂ O
COC ₆ H ₄ COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH
₂ ＣＨCHCH ₂ OCOC ₆ H ₄ COO (CH ₂ ) ₃ Si
(OC ₂ H ₅ ) ₃ , and the like, but is not limited thereto.

The amount of water to be used depends on the trialkoxysilane having a quaternary ammonium group represented by the general formula (4), the trialkoxysilane represented by the general formula (5) and the non-alkoxysilane represented by the general formula (6). The molar amount is at least 1.5 times, preferably 1.8 to 5 times the total molar amount of the trialkoxysilane having a saturated group.

The amount of the acid or the base used is determined based on the amount of the trialkoxysilane represented by the general formula (5) and the trialkoxysilane represented by the general formula (6). The molar amount is not more than 0.05 times the total molar amount.

In the present invention, examples of the acid used include hydrochloric acid, sulfuric acid, acetic acid, formic acid and the like, and bases such as n-butylamine, triethylamine, p-dimethylaminoethanol, sodium hydroxide, potassium hydroxide,
Examples include ethylenediamine and diethylamine. These acids and bases may be used in combination.

Although the reaction proceeds with the above reaction system alone, as the reaction proceeds, the viscosity increases and the stirring efficiency and the efficiency of removing the reaction heat are reduced, so that an organic solvent may be added. At this time, the organic solvent may be a water-miscible one or a water-insoluble one, and is preferably used in common with a solvent used as a coating, so that it can be easily handled later. Become.

For example, alcohols such as propanol and butanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as cellosolve acetate and methyl cellosolve, esters such as ethyl acetate and butyl acetate, toluene and xylene. Aromatic hydrocarbons. These solvents may be used as a mixture of two or more kinds.

The reaction temperature is usually from 20 ° C. to 120 ° C.
The reaction time is 1 to 24 hours. Termination of the polymerization reaction is carried out by neutralizing the reaction solution, and salts generated at that time are removed by filtration or washing with water. Next, coexisting water, alcohol and other low-boiling fractions such as alcohol are distilled off under reduced pressure, and if necessary, the reaction product is further purified by post-treatment operations such as column chromatography and extraction. Silsesquioxane can be obtained.

The antistatic resin composition using the polyorganosilsesquioxane of the present invention can be obtained by blending a monomer and / or macromer containing a polymerizable unsaturated bond in the molecule.

To cure the antistatic resin composition, a photosensitizer for initiating radical polymerization of the resin composition and / or
Alternatively, after mixing the radical polymerization initiator, irradiation with radiation such as ultraviolet rays or heating is performed for a certain time. If necessary, both may be used together.

In the present invention, it is possible to further enhance the ultraviolet curability by using a so-called sensitizing aid such as a tertiary amine together with the above-mentioned photosensitizer. As the tertiary amine, aliphatic, aromatic, various tertiary amines can be used, and N-dimethanolamine, triethanolamine,
N-methyldiethanolamine, triethylamine, P
-Ethyl dimethylaminobenzoate and the like.

The curable resin composition of the present invention may have various properties for the purpose of improving the storage stability and handleability of the composition, improving the physical properties of the cured coating film, or depending on the use of the cured product. Substances and compounds can be blended.

[0035]

The preparation of the polyorganosiloxane having a cationic functional group according to the present invention is not only easy, but it may be used alone, but preferably a coating film cured with a polymerizable monomer is water-resistant. It has excellent durability and provides effective antistatic ability. The surface resistance can be freely adjusted according to the required performance by changing the type and amount of the cationic functional group.

When cured, the coating film is hard and has an antistatic silsesquioxane structure, so that it has extremely excellent water resistance and durability, and has a semi-permanent antistatic effect. Persistently.

[0037]

The present invention will be specifically described below with reference to examples and comparative examples. “Parts” in Examples and Comparative Examples indicates “parts by weight” unless otherwise specified.

Example 1 Synthesis of polyorganosilsesquioxane compound (I) 66.4 parts of γ-aminopropyltriethoxysilane, 89.2 parts of methyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane 49 .6 parts, water 40 parts,
After 0.4 parts of p-methoxyphenol and 200 parts of methanol were charged into the separable flask, the mixture was heated and stirred at 60 ° C. for 4 hours. Subsequently, the mixture was cooled to 10 ° C., and 30.4 parts of a 36% hydrochloric acid aqueous solution was gradually added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the mixture was stirred for 1 hour. Next, the solvent was removed using an evaporator to obtain 117.5 parts of a polyorganosilsesquioxane compound. When the molecular weight of this reaction product was determined by GPC, Mn = 12,30
0, Mw = 74,500. In addition, in the infrared absorption spectrum of the obtained reaction product, the stretching vibration of Si—O—Si having a polyorganosilsesquioxane structure is 103
It has been confirmed to 5cm ^-1 and 1105cm ^-1. The X-ray powder diffraction pattern of this reaction product has a clear diffraction peak at 4.5 °, which is the value measured by Brown et al. For phenylsilsesquioxane (5.0 ± 0.5 °). Matched. This value corresponds to the distance of the repeating unit of the cyclic siloxane (tetramer) in the ladder structure. Further, in the course of the production under exactly the same conditions as in the production method described above, the solution in the middle of the reaction was collected to remove the alcohol by-product, and the number average molecular weight Mn was measured by GPC. For the sample from which Mn was determined, the viscosity in the methyl ethyl ketone solution was measured at various concentrations, and the intrinsic viscosity [η] was measured from the relationship between the reduced viscosity and the concentration. In the same manner, Mn and [η] were measured at several points until the reaction was completed, and the relationship between logMn and log [η] was examined. The gradient was 0.6. It was found that it grew in a shape.
This compound was analyzed by elemental analysis and NMR analysis to determine
A polyorganosilsesquioxane compound (I) having the structural units of (a) to (c);
It was confirmed that the molar ratio of (c) was 3: 5: 2. _{^{Cl - H 3 N + -CH 2}} -CH 2 -CH 2 -SiO 3/2 ( A) CH ₃ -SiO _{3/2 (b) CH 2 = C (CH 3} ) COO-CH 2 CH 2 CH 2 - SiO _3/2 (c)

(Example 2) Synthesis of polyorganosilsesquioxane compound (II) 25.5 parts of N-phenyl-γ-aminopropyltriethoxysilane, 81.7 parts of methyltrimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane 74.4
Parts, 35 parts of water, 0.4 parts of p-methoxyphenol and 300 parts of ethanol after charging into a separable flask.
The mixture was heated and stirred at 0 ° C. for 3 hours. Then cool to 10 ° C,
10.1 parts of a 36% hydrochloric acid aqueous solution was gradually added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the mixture was further stirred for 1 hour. Next, when the solvent was removed using an evaporator, 120.2 parts of a polyorganosilsesquioxane compound was obtained. When the molecular weight of this reaction product was determined by GPC, it was Mn = 3,100 and Mw = 6,800. The stretching vibration of Si-O-Si having a polyorganosilsesquioxane structure was confirmed at 1035 cm ^-1 and 1105 cm ^-1 . The X-ray powder diffraction pattern of this reaction product has a clear diffraction peak at 4.5 °, and the value measured by Brown et al. For phenylsilsesquioxane (5.0 ± 0.5 °).
Matched. This value corresponds to the distance of the repeating unit of the cyclic siloxane (tetramer) in the ladder structure. Further, in the course of the production under exactly the same conditions as in the production method described above, the solution in the middle of the reaction was collected to remove the alcohol by-product, and the number average molecular weight Mn was measured by GPC. Mn
The viscosity in the methyl ethyl ketone solution was measured at various concentrations for the sample obtained, and the intrinsic viscosity [η] was measured from the relationship between the reduced viscosity and the concentration. Similarly, Mn and [η] were measured at several points until the end of the reaction, and the log Mn and log were measured.
Examination of the relationship of [η] revealed that the gradient was 0.7, indicating that the siloxane polymer grew linearly with increasing molecular weight. This compound was analyzed by elemental analysis and N
According to the MR analysis, it is a polyorganosilsesquioxane compound (II) having the following structural units (E) to (F), and the molar ratio of (E) :( E) :( F) is 1: 6: 3
Was confirmed. _{^{Cl - [C 6 H 5 N}} + H 2 -CH 2 -CH 2 -CH 2 -SiO 3/2] ( d) CH ₃ -SiO _{3/2 (O) CH 2 = C (CH 3} ) COOCH 2 CH ₂ CH ₂ —SiO _3/2 (f)

Example 3 Synthesis of polyorganosilsesquioxane compound (III) Formula:

Embedded image 19.6 parts of a compound represented by the formula, 142.6 parts of methyltriethoxysilane, 37.2 parts of γ-methacryloxypropyltrimethoxysilane, 50 parts of 0.001% hydrochloric acid aqueous solution, p
After charging 0.4 part of methoxyphenol and 200 parts of methanol into a separable flask, the mixture was stirred at 40 ° C. for 2 days, heated to 60 ° C., and further stirred for 2 hours. Next, the solvent was removed using an evaporator to obtain 101.6 parts of a polyorganosilsesquioxane compound. When the molecular weight of this reaction product was determined by GPC, Mn = 1,5
00, Mw = 2,300. In addition, in the infrared absorption spectrum of the obtained reaction product, the stretching vibration of Si—O—Si having a polyorganosilsesquioxane structure is 103
It has been confirmed to 5cm ^-1 and 1105cm ^-1. The X-ray powder diffraction pattern of this reaction product has a clear diffraction peak at 4.5 °, which is the value measured by Brown et al. For phenylsilsesquioxane (5.0 ± 0.5 °). Matched. This value corresponds to the distance of the repeating unit of the cyclic siloxane (tetramer) in the ladder structure. Further, in the course of the production under exactly the same conditions as in the production method described above, the solution in the middle of the reaction was collected to remove the alcohol by-product, and the number average molecular weight Mn was measured by GPC. For the sample from which Mn was determined, the viscosity in the methyl ethyl ketone solution was measured at various concentrations, and the intrinsic viscosity [η] was measured from the relationship between the reduced viscosity and the concentration. Similarly, Mn and [η] were measured at several points until the end of the reaction, and the relationship between logMn and log [η] was examined. The gradient was 0.7, and the siloxane polymer became linear with increasing molecular weight. It was found that it grew in a shape.
This compound was analyzed by elemental analysis and NMR analysis to determine
A polyorganosilsesquioxane compound (III) having the structural units of (a) to (e).
It was confirmed that the molar ratio of (g) was 5:80:15.

Embedded image CH ₃ —SiO _3/2 (h) CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ CH ₂ —SiO _3/2 (q)

Example 4 Synthesis of Polyorganosilsesquioxane Compound (IV) 110.7 parts of γ-aminopropyltriethoxysilane,
53.5 parts of methyltriethoxysilane, 29.6 parts of vinylmethoxysilane, 39.3 parts of γ-mercaptopropyltrimethoxysilane, 52.2 parts of water, 300 parts of methanol
The mixture was charged into a separable flask and heated and stirred at 50 ° C. for 3 hours. Subsequently, the mixture was cooled to 10 ° C., and 54.3 parts of trimethylchlorosilane was gradually added dropwise over 1 hour.
After completion of the dropwise addition, the temperature was raised to 40 ° C., and the mixture was stirred for 1 hour. Next, when the solvent was removed using an evaporator, 160.5 parts of a polyorganosilsesquioxane compound was obtained. When the molecular weight of this reaction product was determined by GPC, Mn = 4,7
00, Mw = 18,600. In the infrared absorption spectrum of the obtained reaction product, the stretching vibration of Si—O—Si having a polyorganosilsesquioxane structure was 10%.
It has been confirmed to 35cm ^-1 and 1105cm ^-1. The X-ray powder diffraction pattern of this reaction product has a clear diffraction peak at 4.5 °, which is the value measured by Brown et al. For phenylsilsesquioxane (5.0 ± 0.5 °). Matched. This value corresponds to the distance of the repeating unit of the cyclic siloxane (tetramer) in the ladder structure. Further, in the course of the production under exactly the same conditions as in the production method described above, the solution in the middle of the reaction was collected to remove the alcohol by-product, and the number average molecular weight Mn was measured by GPC. For the sample from which Mn was determined, the viscosity in the methyl ethyl ketone solution was measured at various concentrations, and the intrinsic viscosity [η] was measured from the relationship between the reduced viscosity and the concentration. Similarly, Mn and [η] were measured at several points until the end of the reaction, and the relationship between logMn and log [η] was examined. The gradient was 0.8, and the siloxane polymer became linear with increasing molecular weight. It was found that it grew in a shape. This compound is obtained from elemental analysis and NMR analysis, as described below. It was confirmed that the compound was the silsesquioxane compound (IV), and that the molar ratio of (co) :( sa) :( si) was 5: 3: 2. _{^{CH - H 3 N + -CH 2}} CH 2 CH 2 -SiO 3/2 ( co) CH ₃ -SiO _3/2 (Sa) CH ₂ = CHSiO _{3/2 (Shi) HS-CH 2 CH 2 CH} 2 - SiO _3/2 (S) (CH ₃ ) ₃ SiO _1/2 (C)

[0042]

[Application Examples] Each physical property value in the application examples was measured according to the following methods.

<< Surface Hardness >> The surface hardness was measured according to JIS K5401 using a pencil scratch tester for paint.

<< Surface Individual Resistance Test >> High Resistance Measuring Instrument 43
29A (made by Hewlett-Packard) was used.

<< Half-life of charged voltage >> A voltage of 10 KV was applied using a static honest meter (manufactured by Anato Shokai), and the decay of the charged voltage was measured at the half-life.

<< Water Resistance >> The test piece was immersed in water at 80 ° C., and the surface condition after one hour was visually observed. Furthermore, the surface resistance value and the half-life of the charged voltage were measured.

<< Durability Test >> A test piece was heated at 80 ° C. and 80%
After standing in a humidity atmosphere for 1000 hours, the surface condition was visually observed. Furthermore, the surface resistance value and the half-life of the charged voltage were measured.

(Application Example 1) 15 parts of the polyorganosilsesquioxane (I) obtained in Example 1, 55 parts of pentaerythritol triacrylate, 20 parts of diethylene glycol diacrylate, 10 parts of phenoxyethyl acrylate, 2.5 parts of benzophenone And 2.5 parts of ethyl p-dimethylaminobenzoate were mixed to obtain an antistatic resin composition. The composition was spin-coated on a polycarbonate substrate (disk having a diameter of 12 cm) and applied to a thickness of about 2 μm. Next, the coated test piece was irradiated with a 3 KW high-pressure mercury lamp to complete the curing of the composition on the surface with an irradiation energy of 500 mj / cm ² of ultraviolet light. Table 1 shows the physical properties of the cured film.

(Application Example 2) 40 parts of the polyorganosilsesquioxane (II) obtained in Example 2, 50 parts of dipentaerythritol hexaacrylate, 10 parts of acryloylmorpholine, 2-hydroxy-2-methyl-1 5 parts of -phenylpropan-1-one were mixed to obtain an antistatic resin composition. The composition was treated in the same manner as in Example 1 to form an ultraviolet cured film on a polycarbonate plate. Table 1 shows the physical properties of this film.

(Application Example 3) 100 parts of the polyorganosilsesquioxane (IV) obtained in Example 4, 2 parts of isopropylthioxanthone, and 2 parts of isoamyl p-dimethylaminobenzoate were mixed. The composition was spin-coated on a polycarbonate substrate (disk having a diameter of 12 cm) and applied to a thickness of 2 μm. Next, a UV energy of 1000 m was applied to the coated test piece using a 3 kW high-pressure mercury lamp.
After irradiation with j / cm ² , the composition was heated and maintained at 80 ° C. for 2 hours to complete the curing of the surface composition. Table 1 shows the physical properties of the composition coating.

[0051]

[Table 1]

[0052]

The present invention provides a novel polyorganosilsesquioxane and a method for producing the same.

The novel polyorganosilsesquioxane is useful as an antistatic agent for plastic products as a composition with a monomer or macromonomer having a polymerizable unsaturated bond in the molecule.

Although the composition is easy to apply to products and the like, the cured film has not only an antistatic property but also a high hardness film having excellent scratch strength and abrasion resistance, and It is a useful composition which forms an excellent film which is rich in transparency, gloss and does not lose its performance even under conditions of high temperature and high humidity.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 77/26 C08G 77/20

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (1): R ¹ —SiO _3/2 (1) (wherein R ¹ has 1 to 1 carbon atoms having a quaternary ammonium type cation group as a substituent). 12 substituted hydrocarbon groups), general formula (2) R ² —SiO _3/2 (2) (wherein R ² is an alkyl group having 1 to 3 carbon atoms), and general formula (3) R ^3- SiO _3/2 (3) (wherein, R ³ is an organic residue containing a polymerizable unsaturated bond) The molar ratio of (1) :( 2) :( 3) Is 1 to 80: 5 to 90: 5 to 90 (however, (1) + (2)
+ (3) = 100. A) a ladder-type polyorganosilsesquioxane having a number average molecular weight of 600 to 100,000. 2. A trialkoxysilane represented by the general formula (4), R ¹ —Si (OR ⁴ ) ₃ ... (4) a trialkoxysilane represented by the general formula (5), R ² —Si ( OR ⁵ ) ₃ ... (5) and trialkoxysilane R ³ —Si (OR ⁶ ) ₃ ... (6) represented by the general formula (6) (wherein, R ^{1 to} R ³ are the same as those described above) R ^{4 to} R ⁶ are an alkyl group having 1 to 3 carbon atoms.) And (4), (5) and (6) in a molar ratio of 1 to 80:
5 to 90: 5 to 90 , and (4), (5)
A method for producing a ladder-type polyorganosilsesquioxane, comprising co-condensing 1.5 times or more mols of water with respect to the total mol amount of (6) and an acid or a base. 3. A general formula (4) in some or all of the trialkoxysilane general formula represented ^{(7) R 7 -Si (OR} 8) 3 ...... (7) ( where, wherein R ⁷ is A substituted hydrocarbon group having an amino group as a substituent, and R ⁸ being a co-condensation instead of a trialkoxysilane represented by
Polyorganosilsesquioxane method of manufacturing of claim 2 wherein the quaternary ammonium of the amino group in R ^7.