JPH03103424A - Maleimide resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Summary] With regard to maleimide resin compositions, the purpose is to provide a maleimide resin composition having excellent heat resistance, flexibility, hydrophobicity, crack resistance, etc. A maleimide resin represented by: (in the formula, m is 0 to 6) as a base resin, and a specific epoxy-modified polysiloxane as a flexibilizer is added to 100 parts by weight of the maleimide resin. 5 to 80 parts by weight, 10 to 95 parts by weight of a specific diagonal as a curing agent, and 0.0 to 95 parts by weight of a silicone surfactant represented by the following formula: 2 to 10 parts by weight, respectively, are added.

[Industrial Application Field] The present invention relates to a maleimide resin composition, and more specifically, a maleimide resin composition having excellent heat resistance, toughness, flexibility, hydrophobicity, crack resistance, and chemical resistance. Regarding. Since the maleimide resin assembly of the present invention has the above-mentioned excellent properties, it is used in various fields, especially multilayer lamination resins, conductive pastes, electronic device protective films, adhesives, paints, and sealants. It can be advantageously used in the field of fastening materials and restraining materials.

[Conventional technology]

BACKGROUND ART In recent years, electronics, electrical equipment, transportation equipment, etc. have become smaller, lighter, and more sophisticated, and along with this, materials with excellent heat resistance are desired.

Polyimide resin is generally known as a heat-resistant resin, but since this resin is a dehydration condensation type, voids are likely to occur in the cured product due to condensation water generated during the reaction, and it is difficult to cure. Decreases the reliability of things. On the other hand, since polyimide itself is insoluble and infusible, it is difficult to shape it into a shape.

Maleimide resins such as bismaleimide and polymaleimide are known as polyimides with improved formability. However, since bismaleimide has a high melting point, curing is generally performed at high temperatures and for long periods of time (180 ~
The drawback is that it requires a temperature of 350° C. for 15 to 16 minutes. Furthermore, although the curing temperature of polymaleimide is about 70 to 80°C lower than that of bismaleimide, the cured product has a high crosslinking density and may become crumbly or have large residual strain.
It has the drawback of being brittle and prone to cranking, and an effective method for reducing residual strain is required. Furthermore, bismaleid and polymaleimide cannot guarantee satisfactory curability even if they are used in combination.

Furthermore, in the case of known resin compositions, the obtained cured product is poor in toughness and flexibility, which is another problem. Furthermore, conventional maleimide resins have poor hydrophobicity and have the disadvantage of significantly reducing the reliability of cured products.

As a recent trend, resins with excellent chemical resistance are also required.

[Problem to be solved by the invention]

The purpose of the present invention is to eliminate the drawbacks of the conventional technology as described above; in other words, it is an object of the present invention to provide heat resistance, flexibility, hydrophobicity, crack resistance, and An object of the present invention is to provide a maleimide resin composition with excellent chemical properties.

[Means to solve the problem]

According to the present invention (first invention), the above-mentioned object is achieved by using a maleimide resin represented by the following formula: Me Me
Ah? Me in the formula is a methyl group, and n is 5 to 300
), 5 to 80 parts by weight, diamine represented by the following formula as a curing agent: H2N
10 to 95 parts by weight of -R-Ni+■ (R in the formula represents an alkyl group or aryl group having 1 to 4 carbon atoms), a silicone surfactant represented by the following formula: (in the formula m is O~6
) as a base resin, and an epoxy-modified polysiloxane represented by the following formula as a flexibilizer based on 100 parts by weight of the maleimide resin: (In the above formula, R is the same as defined above. and x, y, a and b are each 200 to 100,000
) is an integer that gives the molecular weight of 0. This can be achieved by a maleimide resin composition characterized by adding 2 to 10 parts by weight of each of these. In addition, in the present specification, when "parts" is hereinafter written, it means "parts by weight."

Furthermore, the above-mentioned object can be achieved by adding 20 to 95 parts of a maleimide resin represented by the following formula (in which R is the same as defined above) according to the following formula; The silicone surfactant represented by: (in the formula, m is the same as defined above) as a base resin, and for 100 parts of the maleimide resin, as a flexibilizer, according to the following formula: Represented diallyl phthalate: (In the above formula, R.x.y, a and b are the same as defined above) at 0. This can be achieved by using a maleimide resin mixture characterized by adding 2 to 10 parts of each.

Furthermore, according to the present invention (third invention), the above-mentioned object is achieved by adding 10 to 60 parts by weight of a maleimide resin represented by the following formula: (l is 1 to 5) and a curing agent. A diamine represented by the following formula: HZN-R
-Nl{z (in the formula, m is the same as defined above) as a base resin, and with respect to 100 parts of the maleimide resin, a fluorine-containing diane expressed by the following formula: (in the formula The G of
a silicone surfactant represented by the following formula: In the above formula, R, x, y, a and b are the same as defined above). be able to.

In the maleic ξ-do resin composition of the present invention, it is essential to use the maleic ξ-do resin shown in the general formula above as the base resin. The described malei ξ resins may be used alone or in combination, and in combination with a flexibilizing agent, a curing agent, a silicone surfactant, which are used at the same time.
Better effects can be achieved.

In the first invention, the maleimide resin compound contains an epoxy-modified polysiloxane having epoxy groups at both ends as shown in the general formula above as a flexibilizing agent. Eboxy-modified polysiloxanes are effective in increasing the toughness and flexibility of the cured product and thus improving crack resistance. If necessary, the epoxy-modified polysiloxane may be used as a prepolymer with a diamine used as a curing agent by pre-kneading it at 50-150'C for 2-30 minutes. Epoxy-modified polysiloxane is added to 1a from 5 to 100 parts per 100 parts of maleimide resin.
Preferably it is added in an amount of 80 parts. This is because if the amount is less than 5 parts, no effect will be exhibited, and if it exceeds 80 parts, the properties of the polyimide as a heat-resistant resin will deteriorate. In addition, methods for adding epoxy-modified polysiloxane include adding it to the main material during the dispersion and mixing stage, or pre-kneading it with the maleimide resin as described above, and then kneading it with other components. Further, the maleimide resin composition according to the first invention is a diamine represented by the following formula: HtN-R-NHt (In the above formula, R represents an alkyl group such as a methyl group or an ethyl group, or a diamine such as a phenyl group. group, represents an aryl group such as tolyl group; other groups may be used depending on the case) as a curing agent. According to the findings of the present inventors, these diagonals not only contribute to the curing of the maleimide resin, but are also effective in eliminating its brittleness and improving its flexibility. Suitable diamines include, for example, 4,4'-diaxinodiphenyl ether, 4,4'-diaxinodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'diaminodiphenyl sulfide. , 4,4'-Diaminodiphenylthioether, orthophenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenyl-2.2'
- Aromatic diamines such as proban, aliphatic diamines such as trimethylene diamine, tetramethylene diamine, hexamethylene diamine, 4,4-dimethylhebutamethylene diamine, and fats such as 1,4-diaminocyclohexane. Examples include cyclic diamines.

Diamines, like the epoxy-modified polysiloxanes described above, can be used in various amounts in maleimide resin compositions. Generally, the blending amount is preferably 10 to 95 parts based on 100 parts of the maleic resin. This is because if the amount of the diamine added is less than 10 parts, the effect of addition will not appear, and if it exceeds 95 parts, the heat resistance of the cured product will deteriorate.

Furthermore, the maleid resin composition according to the first invention contains a silicone surfactant represented by the general formula above. The silicone surfactant imparts hydrophobicity to the cured product and is therefore effective in improving moisture resistance and water resistance. The amount of silicone surfactant is generally as follows:
Preferably, the amount is 0.2 to 10 parts per 100 parts of the maleic resin.

This is because if the amount is less than 0.2 parts, the effect of addition will not be apparent, and if it exceeds 10 parts, it will lead out on the surface of the cured product.

Furthermore, the composition according to the first invention may contain bisphenol A epoxy resin, phenol novolak epoxy resin, Talesol novolac epoxy resin, bisphenol F epoxy resin, and other epoxy resins, as necessary. May be contained. The amount of epoxy resin added is 20 to 600 parts per 100 parts of maleimide resin.
part is preferred. This is because if the amount exceeds 600 parts, the properties of maleimide as a heat-resistant resin deteriorate. Further, when using an epoxy resin, a diamine used as a curing agent for maleimide can be used in combination as a curing agent for the epoxy resin.

In the second invention, the maleimide resin compound contains diallyl phthalate shown in the general formula above as a flexibilizing agent. Diallyl phthalate is effective in improving toughness and flexibility of a cured product when dispersed in a resin matrix. It is desirable to add diallyl phthalate in an amount of 10 to 60 parts per 100 parts of maleimide resin. This is 1
This is because if the amount is less than 0 parts, the effect of addition will not be exhibited, and if it exceeds 60 parts, the heat resistance of the resin will be impaired.

Furthermore, the maleimide resin set according to the second invention e. t1 is
Like the composition according to the first invention described above, it contains the diamine shown in the general formula above as a curing agent. The action of dia ξ and its suitable examples are as described above; however, in the case of this resin compound, the amount of dia≧n is 20 to 95 parts per 100 parts of maleimide resin. preferable. This is because, as in the case of the first invention, if it is less than 20 parts, the effect of addition will not be apparent, and if it exceeds 95 parts, the heat resistance of the cured product will deteriorate.

Furthermore, the maleimide resin composition according to the second invention contains the silicone surfactant represented by the general formula above, similarly to the composition according to the first invention described above.

The action and preferred amount of the silicone surfactant are the same as in the first invention described above.

In the third invention, the maleimide resin composition contains a fluorine-containing diamine having agono groups at both ends. Fluorine-containing diane not only can act as a curing agent for maleic resin, but also improves the chemical resistance, heat resistance, and
It can greatly contribute to improving hydrophobicity and the like. The amount of the fluorine-containing diamine added is preferably 10 to 80 parts per 100 parts of the maleic resin from the viewpoint of chemical resistance, heat resistance, and mechanical properties.

Furthermore, the maleimide resin composition according to the third invention is similar to the composition according to the first and second inventions described above,
Contains the silicone surfactant shown in the general formula above. The action and preferred amount of the silicone surfactant are the same in the first and second inventions described above.

Furthermore, the malegodo resin composition according to the present invention includes:
The following ingredients can be optionally added as needed: (1) Powdered inorganic filler such as fused silica, crystalline silica, alumina, calcium carbonate, etc. The amount of the inorganic filler added is preferably in the range of 30 to 85% by weight of the entire composition. The reason for this is that if the amount of the inorganic filler added is less than 30%, the effect of the addition will not be apparent, and if it is more than 85%, flowability may be reduced, leading to a possibility that workability may be reduced.

(2) A curing accelerator for accelerating the curing reaction of maleimide resin or the curing reaction of epoxy resin (if used) and curing agent. As a curing accelerator, imidazole type such as 2-methylimidazole, phosphine type such as triphenylphosphine, DBU such as phenol salt of DBU
(diazabicycloundecene) type, peroxides such as dicumyl peroxide, etc. are used.

(3) A coupling agent for improving compatibility with the resin when adding an aluminous filler. Examples include silane coupling agents such as 3-acnopropyltriethoxysilane, and titanium coupling agents such as tetraoctyl bis(phosphite) titanate. The amount of the coupling agent added depends on the type and amount of the inorganic filler used, the specific surface area, and the minimum area covered by the coupling agent, but in the present invention, it is preferably 0.1 to 15 parts.

(4) Carnauba wax, stearic acid and its metal salts, monk wax, etc. as mold release agents; brominated epoxy resin, antimony trioxide, etc. as flame retardants; carbon black, etc. as pigments. The maleimide resin composition of the present invention can be prepared by heating and kneading any combination of the ingredients listed above at a temperature of about 60 to 80°C using a commonly used means such as a roll, kneader, or extruder. It can be prepared by Further, in the resin assembly of the present invention, after-cure after processing it into a certain shape is as follows:
It is desirable to perform this in order to complete the curing reaction of the uncured maleimide resin in the cured product.

[For production]

In the maleimide resin composition according to the present invention (first invention), the maleimide resin used as the base resin guarantees heat resistance, and the epoxy-modified polysiloxane used as a flexible agent improves the toughness of the cured product. The diamine used as a curing agent participates in the curing reaction of the polymerimide and eliminates the brittleness of the resin and improves its flexibility, and the silicone surfactant is used as a curing agent to improve flexibility and therefore crack resistance. It imparts hydrophobicity to objects, contributing to improved moisture resistance and water resistance.

〔Example〕

Next, the present invention will be explained with reference to Examples and Comparative Examples.

1-12, 6 1-8 In this example, the following raw materials were used.

Malay ξ resin: Bismaleimide of Mitsui Toatsu■ is expressed by the following formula.

Epoxy modified polysiloxane: Chisso's Cyraplane (molecule IT=1,000).

Dia ξ: Diaminodiphenylmethane from Sumitomo Chemical 9@, which can be produced manually as ξ Cure M.

Silicone surfactant: Nippon Unicar ■ product available as SIIJET L-5310.

Curing accelerator: diazabicycloundecenesanapuroll
Wa"U-CAT SA" Filling material: Silica powder "RD-8" manufactured by Tatsumori ■ By kneading these raw materials in a pressurized double-arm kneader at the ratio listed in Table 1 below, the desired A composite was prepared.

In this example, diamine and epoxy-modified polysiloxane were pre-kneaded to obtain a polymer, which was then kneaded with other components. In addition, the test piece was prepared as follows: First, the composite obtained by kneading was made into an 8 mesh bath powder, this powder was transferred to a press mold,
After compression molding at 180° C. and 80 kg/all for 710 minutes, L and others were then after-cured at 200° C. for 8 hours.

Characteristics of the composition obtained as described above were evaluated as follows: - Glass transition temperature measured using a thermomechanical analyzer (Shinku Riko).

・Bending strength According to JIS K6911.

・Bending elastic modulus According to JIS K6911.

・Evaluate the cross section of the sample (IOX 5 x 30 mm) after cooling with a microscope using a microscope.

・Water absorption rate According to JIS K6911; boiling absorption rate.

- Visually evaluate the surface of the sample (IOX 5 x 30 mm) after bleed-out cooling.

The results obtained are shown in Table 1 below. As a result of the description, especially from Examples 1 to 5 and Comparative Examples 1 to 3, it was found that the toughness of the cured product was improved by adding epoxy-modified silicone, and from Examples 6 to 1O and Comparative Examples 4 to 5, silicone It can be seen that if the addition of the surfactant is less than 0.2 parts, no effect of the addition appears, and if it exceeds 10 parts, bleed-out occurs.

The following margins 113 to 24 and LfLL details were repeated.The methods of Examples 1 to 12 and Comparative Examples 1 to 8 described above were repeated. However, in this example, instead of the epoxy-modified polysiloxane, diallyl phthalate: "Daprene" manufactured by Osaka Soda ■ was used as a raw material, and silica powder was not added.

When the properties of the obtained assembly were evaluated in the same manner as in the above example, the results shown in Table 2 below were obtained. From Examples 13 to 17 and Comparative Examples 9 to 11, the amount of diallyl phthalate added was 10 parts per 100 parts of maleimide.
If the amount is less than 60 parts, the toughness of the cured product will not improve, and if it exceeds 60 parts, the mechanical strength of the cured product at high temperatures will deteriorate. In addition, from Examples 18 to 22 and Comparative Examples 12 to 14, if the amount of silicone surfactant added is less than 0.2 parts, the addition effect does not appear, and if it exceeds 10 parts, bleed occurs on the surface of the cured product. An out occurs. Furthermore, Comparative Example 15. According to No. 16, if the amount of diamine added is less than 20 parts, the addition effect will not appear, and if it exceeds 95 parts, the heat resistance will deteriorate.

25-34 17-2 The methods of Examples 1-12 and Comparative Examples 1-8 described above were repeated. However, in this example, fluorine-containing diamine: 4,4-diaminoperfluorodiphenyl sulfide was used as the raw material instead of epoxy-modified polysiloxane and diane, and silicate powder was not added.

When the properties of the obtained assembly were evaluated in the same manner as in the above example, the results shown in Table 3 below were obtained. Examples 30 to 34 and Comparative Example 17. From 18, the amount of fluorine-containing diamine added per 100 parts of maleimide is
If it is less than 10 parts or more than 80 parts, the mechanical strength of the cured product at high temperatures will deteriorate. From Examples 25 to 29 and Comparative Examples 19 to 21, the amount of silicone surfactant added was as follows:
If the amount is less than 0.2 parts, no effect will be exhibited, and if it exceeds 10 parts, bleed-out will occur on the surface of the shaped article.

[Effects of the Invention] According to the present invention, by making the maleimide resin composition as described in the claims, heat resistance, toughness, flexibility, hydrophobicity, crank resistance and In some cases, it is possible to provide a maleimide resin composition that also has excellent chemical resistance.

Claims (1)

[Claims] 1. Maleimide resin represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (m in the formula is 0 to 6) as a base resin, and the maleimide resin Epoxy-modified polysiloxane expressed by the following formula as a flexible agent for 100 parts by weight of resin: ▲There are numerical formulas, chemical formulas, tables, etc.▼ (Me in the formula is a methyl group, and n is 5 ~300
), 5 to 80 parts by weight, diamine represented by the following formula as a curing agent: H_2
10 to 95 parts by weight of N-R-NH_2 (R in the formula represents an alkyl group or aryl group having 1 to 4 carbon atoms), a silicone surfactant represented by the following formula: ▲ Formula, There are chemical formulas, tables, etc. ▼ (In the above formula, R is the same as defined above, and x, y, a and b are each integers giving a molecular weight of 200 to 100,000) from 0.2 to 10 A maleimide resin composition, characterized in that each part by weight is added to the maleimide resin composition. 2. Maleimide resin expressed by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (m in the formula is 0 to 6) as a base resin, and based on 100 parts by weight of the maleimide resin Diaryl phthalate, which is expressed by the following formula as a flexibilizer: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (l in the formula is 1 to 5), 10 to 60 parts by weight, as a hardening agent. , diamine represented by the following formula: H_2N-
20 to 95 parts by weight of R-NH_2 (R in the formula represents an alkyl group or aryl group having 1 to 4 carbon atoms), a silicone surfactant represented by the following formula: ▲ Numerical formula, chemical formula, There are tables, etc. ▼ (In the above formula, R is the same as defined above, and x, y, a and b are each integers giving a molecular weight of 200 to 100,000) from 0.2 to 10 parts by weight. , a maleimide resin composition comprising the following. 3. Maleimide resin expressed by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (m in the formula is 0 to 6) as a base resin, and based on 100 parts by weight of the maleimide resin The fluorine-containing diamine represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (G in the formula is a group consisting of an alkylene group, a divalent sulfur atom, an oxygen atom, -SO_2-, and a combination thereof. 10 to 80 parts by weight of 10 to 80 parts by weight of a bonding group selected from represents an alkyl group or an aryl group having a carbon atom, and x, y, a and b are each an integer giving a molecular weight of 200 to 100,000). A maleimide resin composition characterized by: