JPS58210955A - Curable resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful as a material for heat-resistant electrical parts, having extremely improved heat-resistant properties, mechanical properties, especially impact resistance, obtained by blending a curable resin with a linear high-molecular weight novolak type substituted phenolic resin and an organic fibrous filler. CONSTITUTION:100pts.wt. curable resin is blended with 10-200pts.wt. substantially linear high-molecular weight novolak type substituted phenolic resin having >=1500 number-average mol.wt. and >=120 deg.C melting point, obtained from 1mol phenolic component consisting essentially of dihydric phenolic component (70- 100mol%) shown by the formula (two of R<1> are H, one or R<1> is 1-8C alkyl, 6-10C aryl, halogen or hydroxyl group; R is H, 1-8C alkyl, halogen or hydroxyl group) and 0.90-1.0mol aldehyde component shown by the formula R<2>- CHO (R<2> is H, methyl, or halogenated methyl) and 10-250pts.wt. organic fibrous filler based on 100pts.wt. total amounts of the two components.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition having excellent heat resistance properties and mechanical properties, particularly impact strength. In more detail,
The present invention relates to a curable resin composition comprising a curable resin, a substantially linear high molecular weight novolac-type substituted phenolic resin, and an organic fibrous filler, and which has significantly improved heat resistance properties, mechanical properties, particularly impact strength.

Curable resins such as various epoxy resins, urethane resins, urea resins, melamine resins, and phenolic resins can be made into curable resin compositions by adding curing agents and, if necessary, various fillers and curing them. It is used in various molded products. However, although these curable resin compositions have excellent mechanical properties at relatively low temperatures around room temperature, they have poor thermal deformation temperature, thermal deformation at high temperatures, bending strength, mechanical strength, dimensional stability, etc. Because of their poor heat resistance and mechanical properties, they cannot be used as molded products under heated conditions.

In order to improve the heat resistance, mechanical properties, and other properties of these curable resin compositions, resol-type phenolic resins or novolak-type phenolic resins and inorganic fillers such as glass fiber and silica are blended as necessary. Many curable resin compositions have been proposed. For example, when the curable resin is an epoxy resin, a curable resin composition prepared by blending the epoxy resin with a novolac type phenol resin and, if necessary, an inorganic filler, is
No. 246, No. 8-11827, No. 39-3
No. 574, No. 39-27769, No. 41-1
352 Publication, 45-ro0ro 51, 46-3
No. 8030, No. 48-8278, No. 48-4
No. 4958, No. 50-19319, No. 51-
No. 20537, No. 51-21679, No. 51
-21839 publication, 51-24399 publication, 51-24399 publication, same 5
1-4!1403, 52-3828, 52-9480, JP-A-48-72296, JP-A-49-118797, JP-A-49-118798
Publication No. 50-70497, Publication No. 50-1084
No. 00, No. 51-132267, No. 52-1
No. 38599, No. 52-144099, No. 5
This method has been proposed in, for example, Japanese Patent No. 5-29532. However, the novolak type phenolic resins blended into the epoxy resin compositions proposed in any of these known documents are all novolak type phenolic resins manufactured by ordinary methods, and their number average molecular weights are at most 1200. Hereinafter, the novolak type phenol resin is usually a relatively low molecular weight of 1000 or less. Even if such a relatively low molecular weight novolac type phenolic resin is blended, the resulting epoxy resin composition will have poor heat resistance properties such as heat distortion temperature, heat distortion at high temperatures, bending strength, mechanical strength, and dimensional stability. Also, it is not possible to sufficiently improve mechanical properties. In addition, even if the curable resin is a curable resin other than epoxy resin, such as urethane resin, urea resin, melamine resin, or phenol resin, even if a relatively low molecular weight novolac type phenolic resin is blended, the curable resin It is not possible to sufficiently improve the heat resistance properties and mechanical properties of the resin composition.

The present applicants have developed a new polymer consisting of difunctional phenol component units as the main component and 1. We found a substantially linear high molecular weight novolak type substituted phenol resin, and further added various curable resins such as epoxy resins and optionally inorganic fillers to this high molecular weight novolak type substituted phenol resin. The curable resin composition can be either a curable resin composition obtained by curing the above-mentioned curable resin alone or a curable resin composition obtained by blending the curable resin with a conventional low molecular weight novolac type phenolic resin and curing it. It was discovered that the heat resistance and mechanical properties were significantly improved compared to
-73754, Japanese Patent Application No. 55-73756, and Japanese Patent Application No. 55-76757. The curable resin composition proposed by the present applicant is extremely excellent in heat resistance and mechanical properties as described above.
In addition, curable resins such as nol resins, which are mainly composed of difunctional phenol component units and have a number average molecular weight (un) of 15
It has been discovered that a curable resin composition containing a substantially linear high molecular weight novolac-type substituted phenolic resin having a molecular weight of 00 or higher and an organic fibrous filler has excellent heat resistance and mechanical properties, particularly impact resistance. invention has been achieved. According to the present invention, the curable resin composition of the present invention has excellent heat resistance properties such as heat distortion temperature, heat distortion at high temperatures, bending strength, mechanical strength, and dimensional stability, and mechanical properties, particularly impact resistance strength. It has the characteristic of being

Furthermore, the curable resin composition of the present invention has significantly higher heat resistance and mechanical properties than a curable resin composition in which a conventional low molecular weight novolac type phenolic resin is blended instead of the high molecular weight novolac type substituted phenolic resin. Furthermore, the heat resistance properties and mechanical properties are significantly superior to that of a curable resin composition that does not contain the high molecular weight novolac type substituted phenol resin.

Further, the curable resin composition of the present invention has been proposed in 1. by the applicant in the above-mentioned publication. Compared to curable resin compositions containing inorganic fillers, this resin composition has excellent impact resistance strength with almost no deterioration in its superior properties such as heat resistance and mechanical properties. Therefore, the curable resin composition of the present invention can be effectively used in fields such as molding materials and coating materials that require heat resistance and mechanical properties, particularly impact resistance.

That is, the present invention provides: (6) a curable resin; (/7) a bifunctional phenol component as the constituent phenol component, and a number average molecular weight <urL> of 150
This is a curable resin composition comprising a substantially linear high molecular weight novolak-type substituted phenol resin having a molecular weight of 0 or more and (C) an organic fibrous filler.

The curable resins blended into the curable resin composition of the present invention include curable resins that are cured with a curing agent and, if necessary, a curing accelerator, and curable resins that are cured by heat. More specific examples include various epoxy resins, various urethane resins, urea resins, melamine resins, polybismaleimide resins, normal novolac type phenolic resins, and normal resol type phenolic resins. Among curable resins (b),
It is preferable to apply the present invention to a curable resin that can be cured with a phenolic hydroxyl group-containing compound because the heat resistance and mechanical properties of the resulting curable resin composition are further improved. More specifically, these curable resins (a)
Among these, it is preferable to use an epoxy resin, a urethane resin, a normal novolac type phenol resin, or a normal resol type phenol resin, since a curable resin composition with further improved performance can be obtained. Furthermore, it is particularly preferable to use an epoxy resin because a curable resin composition with further improved heat resistance and mechanical properties can be obtained.

Among the curable resins (a), epoxy resins [7]
A more specific example will be given below. When the curable resin blended into the curable resin composition of the present invention is an epoxy resin, the epoxy resin is a compound containing two or more epoxy groups in one molecule.

Specifically, such epoxy resins include, for example,
Bisphenol A1 Bisphenol F11゜1.2.2
- Glycidyl ether type epoxy resin of polyphenol compounds such as tetrakis(4-hydroxyphenyl)ethane; Glycidyl ether type epoxy resin of nuclear hydride of the polyphenol compound; Polyhydric phenol type such as catechol, resorcinol, hydroquinone, phloroglucin Glycidyl ether type epoxy resin; Glycidyl ether type epoxy resin of polyhydric alcohols such as ethylene glycol, butanediol, glycerol, erythritol, and polyoxyalkylene glycol; Novolac type epoxy resin; Vinyl cyclohexene dioxide, limonene dioxide, dicyclo Alicyclic epoxy resins such as pentadiene oxide; polyglycidyl ester epoxy resins of ester condensates of polycarboxylic acids such as phthalic acid and cyclohegysan-1,2-dicarboxylic acid; polyglycidylamine epoxy resins: methyl-ebichloro type Examples include epoxy resin.

Among these epoxy resins, it is preferable to use glycidyl ether type epoxy resins of polyphenol compounds or novolac type epoxy resins.

As a curing agent that may be added as necessary to an epoxy resin composition containing these epoxy resins, any compound generally known as a curing agent for epoxy resins can be used. For example, specifically, chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylene diamine, and diethylaminoprobylamine; cycloaliphatic chiliamine; aliphatic polyamine adduct; ketoimine: modified fat polyamine; polyamide amine; aromatic amine; aromatic modified amine; aromatic modified polyamine; tertiary amine curing agent; mercaptan curing agent; acid anhydride curing agent; ethylene-maleic anhydride Copolymers with acid anhydride groups such as polymers; Compounds with phenolic hydroxyl groups such as novolac-type or epoxy-type phenol resin initial condensates; Dicyandiamide; Compounds such as melamine. can.

The high molecular weight novolac-type substituted phenol resin (11) to be blended into the curable resin composition of the present invention has a bifunctional phenol component as the constituent phenol component, and has a number average molecular weight [N,N-dimethylacetamide solvent The value measured by vapor pressure osmosis method (#J:] is 150
0 or more and is a substantially linear high molecular weight novolac-type substituted phenol resin.

In the present invention, the high molecular weight novolac type substituted phenolic resin (/l) (hereinafter sometimes simply referred to as high molecular weight novolac type resin) which is a compounding component may consist entirely of substantially linear novolac repeating units. Alternatively, for each block of novolac type repeating units having a number average molecular weight of 250 to 12,000, a chain extending group consisting of a divalent hydrocarbon group is added from 0.5 to less than 1 mol, particularly from 0.6 to less than 1 mol, per 41 mol of the blower. A high molecular weight novolac-type substituted phenol resin may be used, in which the resins are alternately contained in such a proportion. What is important is that this high molecular weight novolac type resin is substantially linear and has a number average molecule -Jl [J/rL] of 1,000 or more, preferably in the range of 1,700 to 15,000, particularly preferably in the range of 2,000 to 10,000. be. Here, the number average molecular weight is N, N
- Values measured by vapor pressure osmometry in dimethylacetamide solvent. In addition, here, in practice, the meaning of
It means that the polymer chain has a linear structure having a linear or branched structure, and it means that the network structure (ie, gelled product) is not substantially supported.

The number average molecular weight of the high molecular weight novolac type resin (B') is in the range of <1500 or more as described above, but if the number average molecular weight of the resin becomes large, heat resistance and mechanical properties will deteriorate when blended into a curable resin. It is possible to obtain a composition with excellent mechanical properties, especially impact strength, so it is suitable for
The molecular weight distribution of the high molecular weight novolac type resin is such that the content of resin components having a number average molecular weight of 2000 or more is usually 50% by weight or more, preferably 60% by weight or more, and particularly preferably 70% by weight or more. . In addition, number average molecular weight (weight average molecular weight (M) to pool, ratio of weight (Mtn
The molecular μ distribution expressed as /M is preferably in the range from 1.8 to 20, particularly preferably from 2 to 1°.

In addition, the melting point of the core high molecular weight novolac type resin is usually 12
The range is 0C or more, preferably 150C or more.

The novolac type repeating unit constituting the above-mentioned Takatoto Shikei novolac type resin (in the formula , two of the six RIs are hydrogen atoms, and the remaining one is an alkyl group having 1 to 8 carbon atoms, and 6 RIs.
1 to 10 aryl group, halogen atom, or hydroxyl group 1-1 preferably represents an alkyl group having 1 to 8 carbon atoms [7, more preferably methyl group, ethyl group, isopropyl group, 5 (5) It represents one type of substituent selected from the group consisting of -butyl group, tert-butyl group, and octyl group, and particularly represents a suitable methyl group. Further, R represents the same or different group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, and a hydroxyl group, and preferably one of the two R is a hydrogen atom. The remaining one represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and particularly preferably two R's each represent a hydrogen atom. ) at least 1
The difunctional phenol component of the species ranges from 70 to 100 mol, preferably 80 to 100 mol, particularly preferably 90 to 100 mol, and the trifunctional phenol component ranges from 70 to 60 mol, preferably 0-1.
Ω- to 20 molar, and <K preferably in the range of 0 to 10 molar (provided that the gold side of both phenolic components is 100 molar
Choose so that it becomes morchi. ), and the aldehyde component (11) constituting this is a phenol component consisting of the general formula [I]R"-CR
O [11) (wherein R2 represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and a halogenated methyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom ) is at least one aldehyde component represented by

In this novolac type repeating unit, the bifunctional phenol component is a hydroxyarylene unit represented by the general formula [1] (where RI and R each represent the same group as above) in the resin molecule. It exists as a hydroxyaryl unit represented by the general formula [1v] (where RI and R each represent the same group as above.9) at the molecular terminal of the polymer. The trifunctional phenol component also exists in the resin molecule as a hydroxyarylene unit, similar to the general formula CI), and at the molecular end of the resin, it exists as a hydroxyaryl unit, similar to the general formula [IV]. .

Further, the aldehyde component constituting the high molecular weight novolac type resin has the general formula [■] 7? ! -cg< (V) (wherein, R2
represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and a halogenated methyl group. ) exists as an alkylidene unit. Further, the structure of the novolac type repeating unit is such that the hydroxyarylene units and the alkylidene units are alternately arranged in a double chain structure.More specifically, the structure of the high molecular weight novolac type resin is that the constituent components The phenolic component of is expressed by the above general formula [
When the resin contains only the difunctional phenol component represented by [I], the resin is linear, but if the content of the trifunctional phenol component increases, it may become branched.

The ratio of the aldehyde component to all phenolic components constituting the high molecular weight novolac type resin is usually 0.90 to 1.0 mol per 1 mol of all phenolic components,
Preferably it is in the range of 0.96 to 1.0 mol. The high molecular weight novolac type resin usually does not contain a methylol group, but it contains 0.0 methylol group per mole of all phenolic components.
There is no problem even if it contains a trace amount of methylol group of 1 molar equivalent or less.

Among the phenolic components constituting the high molecular weight novolac type resin (IJ), the bifunctional phenolic component is
It is a phenol represented by the above general formula [1] and has two active hydrogen atoms for substitution reaction on the benzene nucleus. 1 to 8 carbon atoms in the ortho or rose position
These are phenols having an alkyl group, an aryl group having 6 to 10 carbon atoms, a halogen, or a hydroxyl group. More specifically, the following ortho isomers or para isomers of phenols can be exemplified. Even C, cresol, ethylphenol, n-propylphenol,
Inglobilphenol, 7'Tylphenol,
To methylphenol, t^t-butylphenol,
Ortho or para isomers of phenols such as alkylphenols such as pentylphenol, hexylphenol, heptylphenol, and octylphenol; halogenated phenols such as fluorophenol, chlorophenol, and bromophenol; and arylphenols such as phenylphenol and tolylphenol. I can give an example. Other bifunctional phenol components represented by the general formula [1] include 2.3-xylenol, 3.4-xylenol, 2.5-xylenol,
i 1,000 ≠ Tomi-#; 2,5-diethylphenol, 2,5-
Examples include diisopropylphenol, 3.4-dichlorophenol, 2.5-dichlorophenol, and 2-methyl-5-phenylphenol.

The bifunctional phenol component constituting the high molecular weight novolak-type substituted phenol resin is at least one of the above-mentioned phenolic components, and may be a mixture of two or more.

The high-molecular-weight novolac-type resin (the high-functionality phenol component constituting the novolac-type repeating unit) is a phenol having three active hydrogen atoms for substitution reactions on the benzene nucleus, and specifically, These are phenol, meta-substituted phenol, and 3.5-substituted phenol.The substituents that these trifunctional phenols have at the meta-position or 6.5-position include alkyl groups, ), rogens or hydroxyl groups. Among these trifunctional phenols, preferred trifunctional phenols have the general formula (wherein
R represents the same or different substituents selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen, and a hydroxyl group. ) is a phenol represented by More specifically, phenol, m-cresol, m-ethylphenol, m-rt-propylphenol, m-
Isopropylphenol, m-n,-butylphenol, m-butylphenol, rn-tart-butylphenol, m-pentylphenol, m-hexylphenol, m-hebutylphenol, m-octylphenol, m-fluorophenol, m-chlorophenol /
L/, metastatic phenols such as resorcinol: 6,5
-xylenol, 6,5-diethylphenol, 3.5
-Diimpropylphenol, 6.5-dibutylphenol, filtrate, 5-diethylphenol, filtrate, 5-diethylphenol, 3,5-diethylphenol, 6,5-dioctylphenol, 3.5-dichlorophenol, 3
15-dichlorophenol, 6°5-disubstituted phenols, etc. are given as examples. Furthermore, among these trifunctional phenol components, one of the two R's in the above general formula [■] is a hydrogen atom, and the other one is a hydrogen atom, and the number of carbon atoms is 1 to 8. Preferably, it is a phenol represented by an alkyl group or chlorine, and one of the two R
Particularly preferred is a phenolic component in which each of the phenol atoms is a hydrogen atom and the other one is a hydrogen atom, a methyl group, an isopropyl group, a butyl group, a tert-butyl group, or an octyl group.

The aldehyde component constituting the novolak repeating unit is represented by the general formula [n).

Specific examples of these aldehyde components include formaldehyde, acetaldehyde, monochloroacetaldehyde, dichloroacetaldehyde, and trichloroacetaldehyde. Among these aldehyde components, formaldehyde or acetaldehyde is preferred, and formaldehyde is particularly preferred. These aldehyde components exist in the high molecular weight novolak type substituted phenol resin as alkylidene groups represented by the general formula [■].

The polymer novolak type resin (/3) blended into the curable resin composition of the present invention may consist only of novolac type repeating units consisting of the phenol component unit and the aldehyde component unit as described above. Furthermore, as mentioned above, each block of the novolac type repeating unit (α) whose number average molecule it [&n] is usually in the range of 250 to 1200 [chain extending group or bridging group consisting of a divalent hydrocarbon group (hereinafter referred to as , sometimes referred to as chain extender component units).

To explain more specifically the structure of the substantially linear high molecular weight novolac type resin (/7), this type of resin has a relatively low molecular weight and substantially linear novolac type repeating unit block (α) and a chain. Extender component unit <h
The novolac-type repeating unit block (α) and the chain extender component unit (b) are alternately arranged and connected to form a polymer bone, and the novolac-type repeating unit block (α) It is unique in that the repeating unit block (α) is connected. Among this type of high molecular weight novolac type resins, the resin with the simplest molecular structure is a resin in which two molecules of the novolac repeating unit block (α) are linked by one molecule of the chain extender component unit (h) K. , then a resin in which the novolak type repeating unit block (a) of the filtration molecule and two molecules of the chain extender component unit (h) are arranged and connected in an alternating manner, four molecules of the novolac type repeating unit block (α), and A resin in which 6 molecules of the chain extender component units (A) are arranged and linked in an alternating manner, and similarly the novolak-type repeating unit block (a) of 1 molecules and <n-
1) A resin in which the chain extender component units (15) of the molecule are alternately arranged and connected can be exemplified.

The high molecular weight novolac type resin blended into the curable resin composition of the present invention is schematically represented by substantially the general formula [VII) Z(-)'-Z-3-, LYp-Z [V
Il) (wherein Z represents a block of substantially linear novolak-type repeating units formed by condensation of the phenolic component and the aldehyde component, and Y represents a chain extender component consisting of a divalent hydrocarbon group) unit, ρ is an integer of 0 or 1, LE is 0 or 1, and LE is a number on 1''). In the high molecular weight novolac type resin, when the novolak type repeating unit blocks are alternately bonded by the chain extender component units, p is 1, and the chain extender component unit consists only of the novolac type repeating units. In effect (
(Appearance is above) If not included, p is O.

The chain extender component unit (chain extender or bridging group) constituting the high molecular weight novolac type resin [B] is a divalent hydrocarbon group as described above, and further has 1 to 1 carbon atoms.
6 hydrocarbon group, more specifically alkylidene group, alkylene group, cycloalkylene group, cycloalkylidene group, arylalkylidene group, arylalkylene group, arylenebisalkylene group [-R''-A r
-R'-) can be exemplified. Examples of the alkylidene group include a methylene group, ethylidene group, propylidene group, butylidene group, and pentylidene group. Specific examples of the alkylene group include ethylene group, propylene group, isopropylene group, methylene group, pentyline group, and hexylene group. Specific examples of the cycloalkylene group include a cyclobenzene group, a cyclohexylene group, a methylcyclohexylene group, and the like. Specific examples of the cycloalkylidene group include a cyclopentylidene group, a cyclohexylidene group, and a methylcyclohexylidene group. Specifically, the aryl alkylidene group is
Examples include benzylidene group, O-xylidene group, m-xylidene group, and P-xylidene group. Specifically, the arylalkylene group includes a styrene group, α-
Examples include methylstyrene group and ρ-methylstyrene group. Specifically, the arylene bisalkylene group includes O-xylylene group, m-xylylene group, p-
Examples include xylylene groups. Among these chain extender component units <h>, alkylidene groups, alkylene groups, cycloalkylidene groups, cycloalkylene groups, arylalkylidene groups, arylalkylene groups, and arylenebisalkylylene groups are preferable, particularly carbon Alkylidene group having 1 to 4 carbon atoms, alkylene group having 2 carbon atoms, arylalkylidene group having 7 to 9 carbon atoms, arylalkylene group having 8 to 10 carbon atoms, or arylene bisalkylene group having 8 to 10 carbon atoms It is preferable that However, if the molecular weight of these chain extender component units (h) becomes too large, the melting point of the resulting high molecular weight novolak-type substituted phenol resin will decrease and the flexibility will increase, so this resin cannot be used as a hardening type. Even when used as a resin compounding agent, it becomes difficult to obtain a curable resin composition with excellent heat resistance and mechanical properties. Therefore, the molecular weight of these chain extender component units (b) is usually 14 to 200, preferably 14 to 170.
is within the range of

The high molecular weight novolak type resin [A] to be blended into the curable resin composition of the present invention is a new substance and can be produced, for example, by the following method.

That is, (A(1) General formula [1) (In the formula, two of the six R's are hydrogen atoms, and the remaining one is a delkyl group having 1 to 8 carbon atoms, and 6 R's.
1 to 10 aryl groups, ).logen atoms, or hydroxyl groups, and R represents the same or different groups selected from the group consisting of hydrogen atoms, C1-C8 alkyl groups, norlogen atoms, and hydroxyl groups. ) Phenols mainly composed of at least one type of difunctional phenol represented by (11) A phenol component mainly composed of the above difunctional phenol and general formula [11] % formula % [ (in the formula , R1 represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and a ].rogenated methyl group.

) and a novolac-type substituted phenol resin having a number average molecular weight in the range of 250 to 1200; A resol-type substituted phenolic resin consisting of a phenol component mainly consisting of functional phenols and the aldehyde component and having a number average molecular weight in the range of 250 to 1200, aldehyde, (φ ketone, (φ
A chain extender selected from the group consisting of diols and υresinolides [where reactant (a) is a phenol (1
), the chain extender CB) is a resol-type substituted phenolic resin (11). ] in the presence of an acidic catalyst, with the difunctional phenol accounting for at least 70 moles of the phenolic component in the final novolac-type substituted phenolic resin, and in an N,N-dimethylacetamide solvent by vapor pressure osmometry. It is produced by condensing the final novolak type f7) converted phenolic resin to a point where the number average molecular weight reaches a range of 1500 or more.

The blending ratio of the substantially linear polymeric firefly novolac type substituted phenol resin to be blended into the curable resin composition of the present invention is usually in the range of 10 to 200 parts by weight based on 100 parts by weight of the curable resin. , 60 to 150 parts by weight is particularly preferred since the heat resistance and mechanical properties of the cured resin composition are further improved.

The curable resin composition of the present invention contains an organic fibrous filler. Specifically, the organic fibrous filler (C) blended into the curable composition of the present invention includes polyterephthalo-
Fully aromatic polyamides such as il-ρ-phenylenediamine, polyterephthaloyl isophthaloyl-ρ-phenylenediamine, polyisophthaloyl-ρ-phenylenediamine, polyisophthaloyl-m-phenylenediamine,
Nylon 66, Nylon 6, Nylon 10, Nylon 1
Polycondensation type synthetic fibers such as polyamide fibers such as 2, polyamideimide fibers, polybenzimigsol fibers, polyester fibers such as polyethylene terephthalate and poly-1,4-butylene terephthalate; polyvinyl alcohol type synthetic fibers, polyacrylonitrile, etc. Examples include addition-polymerized synthetic fibers such as acrylic fibers; natural fibers such as cotton, hemp, flax, wool, and raw silk. Among the organic fibrous fillers, it is preferable to blend an organic synthetic fibrous filler, and it is particularly preferable to blend a filler made of polycondensed synthetic fibers, especially a fibrous filler made of wholly aromatic polyamide. It is preferable to blend. The organic fibrous filler←゛) can be used in any of the usual single fiber, strand, and cross shapes. The thickness of the fibers of these organic fibrous fillers (0) is usually in the range of 6 to 720μ, preferably in the range of 5 to 15μ. Continuously shot U, 1 to m, 0.3 to 0.6 cm. ) and the sum of the high molecular weight novolak type resin (#)! 10
The amount is usually 10 to 250 parts by weight, preferably 20 to 200 parts by weight, and particularly preferably 25 to 150 parts by weight. The organic fibrous filler (
When C') is a cloth-like material or a strand-like material, the curable resin (6) and the high molecular weight novolak resin (17) are impregnated with the organic fibrous filler in the form of a face, and then this The impregnated product can be molded by heating and curing to obtain a molded product made of the composition of the present invention. When the organic fibrous filler (0) is in the form of a single fiber or a strand, it can be blended by a conventionally known blending method.

It is a filler or an inorganic filler that is added to the curable resin composition of the present invention as necessary. Inorganic fillers (specifically, υ include silica, silica/alumina, alumina, glass powder, glass beads, glass fiber, asbestos, mica, graphite, carbon fiber, titanium oxide, molybdenum disulfide, beryllium oxide, magnesium oxide, Examples include calcium oxide, magnesium hydroxide, calcium hydroxide, talc, heptalite, metal powder, metal fiber, etc. Any of these inorganic fillers may be blended17.
The heat resistance and mechanical properties are also improved. Among these inorganic fillers, heat resistance properties are further improved when glass fiber, carbon fiber, asbestos, etc. are blended, and abrasion resistance is further improved when graphite, titanium oxide, divalent molybdenum oxide, etc. are blended. Arc resistance is further improved by blending mica, asbestos, glass powder, etc., electrical properties such as conductivity are improved by blending p-pump rack, metal fiber, metal powder, graphite, etc., and alumina, titanium oxide, Thermal conductivity is improved by adding Betium oxide, IJium oxide, etc. The blending ratio of these inorganic fillers varies greatly depending on the type of curable resin blended into the curable resin composition, the type of the inorganic filler, and the purpose of use of the resin composition. The range is usually 10 to 250 parts by weight, preferably 60 to 20 parts by weight.
0 parts by weight, particularly preferably in the range from 60 to 150 parts by weight.

The curable resin composition of the present invention includes the curable resin (a)
, In addition to the substantially linear high molecular weight novolac type resin (Kon, the flame retardant @), the inorganic filler (υ
Furthermore, various compounding agents are added as necessary. For example, when the curable resin is a resin that can be cured with a curing agent, the curing agent, curing accelerator, flame retardant, heat stabilizer, antioxidant, lubricant, the inorganic Fillers other than the filler may be added as necessary. Among these compounding agents, as for the curing agent, the above-mentioned high molecular weight novolac type resin (in case it can serve as a curing agent for the above-mentioned curable resin (a)) is an essential component of the curable resin composition of the present invention. If necessary, a curing agent other than the high molecular weight novolac type resin may be added to the curing agent.Also, if the high molecular weight novolac type resin (g) cannot be a curing agent for the curable resin (b), The above-mentioned curing agent is usually blended into the curing agent.The various compounding agents blended as necessary vary depending on the type of the curable resin and the use of the composition, and may include conventionally known compounding agents. Furthermore, the proportions of the various compounding agents blended as necessary vary depending on the type of the curable resin and its use, and appropriate amounts are blended.

The curable resin composition of the present invention is characterized by extremely excellent heat resistance properties such as heat distortion temperature, heat distortion at high temperatures, bending strength, mechanical strength, and dimensional stability, and mechanical properties, particularly impact strength. Since the resin composition of the present invention has particularly excellent heat resistance and impact resistance, it is particularly useful as a material for electrical parts such as printed circuit boards and switchboards that require heat resistance.

Next, the curable resin composition of the present invention will be specifically explained with reference to Examples.

Tables 1 and 2 show the properties of the novolak phenolic resins used in the Examples and Comparative Examples.

Examples 1 to 27. Comparative Examples 1 to 39 The high molecular weight novolak substituted phenolic resins obtained in Reference Examples 1 to 26 or the ordinary low molecular weight novolac substituted phenol resins used as raw materials in the reference examples were used as curable resins. The performance of the curable resin composition was evaluated when it was blended with. Flame retardancy was evaluated using the UL94 method, and other physical properties were evaluated using conventional methods.

When evaluating the performance of the curable composition, one of the following methods was used to prepare the curable resin composition. [Table 6
reference〕.

Preparation method of curable resin composition [A] The Novosic type substituted phenol resin 15f1 bisphenol A type epoxy resin for testing shown in Table 6 (manufactured by Mikata Petrochemical Epoxy Co., Ltd., trade name: EPOMIK 7?-1)
40) 25 f, filler BF listed in Table 6, ・2-
Methylimidazole complex 0.252, Montan acid wax 0.75 F and tetrabromobisphenol A 2.7? as flame retardant. , antimony trioxide (1.21 g) and kneaded on an 80C roll. 7-100 after cooling
Pulverized into mesh and 100 Kq/c in a 250C mold
Press molding was carried out at rA (actual pressure) for 20 minutes. This is 25
After post-curing for 60 minutes at DC, the physical properties of the molded product were measured and the results shown in Table 6 were obtained.

Preparation method of curable resin composition [B] Novolak type substituted phenol resin 15f1 bisphenol A type epoxy resin for test shown in Table 6 (manufactured by Mikata Petrochemical Epoxy Co., Ltd., trade name EpOMIK R-14)
0) 25 t, filler BF3.2-methylimidazole complex 0.25v1 montanic acid wax 0.759 as listed in Table 6 and brominated bisphenol A type epoxy resin as flame retardant (bromine content 16.2% by weight) 981
and 1.22% of antimony trioxide were blended and kneaded for 7 minutes on an 80C roll. After cooling, 7~
Crush into 100 meshes and produce 100kg in a 250C mold.
/Cl7f (actual pressure) for 20 minutes. After post-curing this at 250C for 60 minutes, the physical properties of the molded product were measured and the results shown in Table 6 were obtained.

Preparation method of curable resin composition [C] The high molecular weight ρ-cresol formaldehyde m shown in Table 6 was added to a cloth made from an organic synthetic fibrous filler.
Oil 57V, bisphenol A type epoxy resin (manufactured by Mikata Petrochemical Epoxy Co., Ltd., trade name EPOJflC/!-140
) 659 and brominated bisphenol A type epoxy resin (bromine content 22.0% by weight) as a flame retardant6.
A mixture consisting of 2f and antimony trioxide 2, Of is
- After impregnating Fes dissolved in 100 g of methylpyrrolidone and press-molding in 1Ar at 170C, i.
Q: I made a laminate by post-curing it. The bending strength of this laminate was measured at 2IC and 180C, and the results shown in Table 6 were obtained.

The novolac type substituted phenol m fat 15f for the test shown in Table 6, the novolac type phenol epoxy resin (
Nippon Kayaku Co., Ltd., trade name epoxidized phenol novolac EPPN-201) 25f, filler shown in Table 3, BF
0.25 f of 3,2-methylimidazole complex, 0.75 f of montan acid wax and 2.7 f of tetrabromobisphenol A and 1.2 f of antimony trioxide as flame retardants.
A mixture consisting of f was blended and kneaded for 7 minutes on an 80C roll.

After cooling, it was crushed into 7 to 100 meshes and press-molded in a 250c mold at 100 Kq/cr/i (actual pressure) for 20 minutes. After post-curing this at 250C for 30 minutes, the physical properties of the molded product were measured and the results shown in Table 6 were obtained.

Preparation of curable resin composition [E] The novolac-type substituted phenol resin 151 for testing shown in Table 6, bisphenol A-type epoxy resin (manufactured by Mikata Petrochemical Epoxy Co., Ltd., trade name EpOMIK R-, 14)
0) 25f, filler shown in Table 3, BF3.2-methylimidazole complex 0.25f.

Montan acid wax 0.75 f and brominated bisphenol A type epoxy resin as flame retardant (odor 1 content 1
6.2% by weight) 9.8 t and antimony trioxide 1.
Blend a mixture consisting of 2f and roll on an 80c roll.
Knead for a minute. After cooling, it is crushed into 7 to 100 meshes and molded in a 250C mold at 100 Ky/ad (actual pressure), 20
Press molded for minutes. After post-curing this at 2500 for 60 minutes, the physical properties of the molded product were measured (7) and the results shown in Table 6 were obtained.

The novolak-type substituted phenol resin 402 for testing shown in Table 6, and the novolak-type phenol formaldehyde resin 601 obtained in Comparative Example 2 as the curable resin.
[However, in the comparative example, the novolak-type substituted phenol formaldehyde resin for the test was not used, and the amount of the novolak-type phenol formaldehyde resin used in Resin 8 shown in the coating 1 was 10Of. ], hexamine 10v as a hardening agent, the filler shown in Table 6, stearic acid bisamide 12 as an additive, and tetrabromobisphenol A as a flame retardant 7. Of was blended to prepare a composition for molding material. Thoroughly grind and mix this composition,
The mixture was kneaded for 18 minutes at a temperature of ~110C, and the mixed sheet was pulverized and mixed to obtain a molding material. This is 165
C, 300 Ky/cA.

Table 6 shows the physical properties of the molded product obtained by molding for 5 minutes.

Preparation method of curable resin composition [G] The novolac type substituted phenol resin 702 for testing shown in Table 6, the solid resol type phenol formaldehyde resin 601 prepared in Reference Example 1 as the curable resin,
Stearic acid e-samide 1 as a filler additive shown in Table 3? and Tris (dichloroglobil) as a flame retardant.
Phosphate 2.02 was blended to prepare a composition for molding material.

This composition was sufficiently pulverized and mixed and roll-kneaded at 120C for 15 minutes, and the sheet after the cross-wiring was pulverized and mixed to obtain a molding material. This was molded under the conditions of 180 υ, 300 Ky/crA, and 5 minutes, and the physical properties of the molded product obtained are shown in Table 6.

Diagnosis Example 1. (Production of solid resol type phenol-formaldehyde resin) Phenol 10.0r (11 mol, 67% by weight formalin 90r (RCHO 1.1 mol) and 25 mol)
Put 0.52% ammonia water into the reactor and increase the
The reaction was carried out under reflux for 15 hours at C. Then, it was cooled to room temperature, the separated aqueous layer was removed, and the emulsion of the initial condensate was again dehydrated under reduced pressure while warming to 90 to 110 tl:'. When the temperature of the reactant reached 11 DC, the contents were taken out, cooled and solidified to obtain resin 1002. The number average molecular weight (Mn) of this resin measured by gel reaction chromatography was 440, the weight average molecular weight (Af!) was 740, and the molecular weight distribution (Mn) was 440.
) 1.69, and the melting point was 105t:' as measured by diaphragm microscopy.

Claims (1)

[Scope of Claims] (1) (a) Curable resin, (IJ) mainly consisting of a bifunctional phenol component as a constituent phenol component, and having a number average molecular weight (AfrL) of 15
A curable resin composition comprising: a substantially linear high molecular weight novolac-type substituted phenol resin having a molecular weight of 0.00 or more; and an organic fibrous filler. (2) The high molecular weight novolac-type substituted phenol resin (B) has the general formula [[]R 1 (in the formula, two of the three R's are hydrogen atoms and the remaining 1 is an alkyl group having 1 to 8 carbon atoms, 6 carbon atoms
to 1D aryl group, halogen atom, or hydroxyl group, and R represents the same or different group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, and a hydroxyl group. ) of at least 1 ffl of a difunctional phenolic component represented by at least 70
The phenol component containing at least the molar ratio and the general formula 01) % formula %) (wherein R2 represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and a halogenated methyl group.2
The polymeric novolak-type substituted phenolic resin contains substantially linear novolak-type repeating units formed by condensation with at least one aldehyde component represented by Each block of may contain chain extending groups consisting of divalent hydrocarbon groups alternately in a proportion ranging from I) 0.5 to less than 1 mol per mol of the novolac repeating unit, and the high molecular weight novolac Type-substituted phenolic resin N
The curable resin composition according to claim 1, wherein the curable resin composition has a number average molecular weight of 1,500 or more as measured by vapor pressure osmosis in an N-dimethylacetamide solvent. (3) High molecular weight novolac type substituted phenol resin (c)
is substantially the general formula (to)] Z+Yp-Z)-Y-Z] (wherein Z is a substantially linear novolak-type repeating unit formed by condensation of the phenolic component and the aldehyde component) block, Y represents a chain extending group consisting of a divalent hydrocarbon group, p represents an integer of O or 1, and L represents an integer of 0 or 1 or more. Claim No. (
The curable resin composition according to items 1) to 2). (4) In the general formula l), p is 1, and the chain extension group Y is an alkylidene group having 1 to 4 carbon atoms, an alkylene group having 2 to 5 carbon atoms, an aryl alkylidene group having 7 to 9 carbon atoms, The curable resin composition according to claim 3, which is an arylene bisalkylylene group having numbers 8 to 10. (5) Claims (1) to (4) wherein the phenol component constituting the high molecular weight novolak-type substituted phenol resin is a phenol component containing up to 30 molar trifunctional phenols. Any of the curable resin compositions described in 1. (6) High molecular weight novolak type substituted phenol resin (b)
The blending ratio is 60 to 100 weight of the curable resin.
Or 150! The curable resin composition according to any one of claims (1) to (5), wherein the amount is in the range of parts. (Claim 1) The curable resin (b) is a curable resin that can be cured with a phenolic hydroxyl group-containing compound, and the skeleton composition contains the molecular weight novolac-type substituted phenolic resin as a curing agent. The curable resin composition according to any one of claims to (6).(8) The curable resin composition according to any of claims (1) to (6), wherein the curable resin (6) is an epoxy resin. The curable resin composition according to any one of claims (1) to (6), wherein the curable resin (3) is a resol type phenolic resin or another novolak type phenolic resin. ) The curable resin composition according to any one of claims (1) to (1), wherein the organic fibrous filler (C) is a fibrous filler made of polycondensed synthetic fibers. Any of the compositions described in item 9). (11) The blending ratio of the organic fibrous filler (C) is the total type of the curable resin (3) and the high molecular weight novolac type substituted phenol resin (B) - Jft100 The composition according to any one of claims (1) to αQ, in a range of 10 to 250 parts by weight.