JPS5811551A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having remarkably improved heat resistances, mechanical properties, and flame retardancy, by compounding a specific essentially liner high-molecular novolac-type substituted phenolic resin and a flame retardant to a curable resin. CONSTITUTION:The objective composition is prepared by mixing (A) a curable resin such as epoxy resin, urethane resin, etc., (B) an essentially linear novolac- type substituted phenolic resin having a number-average molecular weight of >=1,500 and containing a bifunctional phenolic compound as a major part (preferably 90-100mol%) of the constituent phenolic component, (C) a flame retardant preferably an organic halogen compound, phosphorus compound, etc., and if necessary, (D) an inorganic filler. The component (B) is e.g. a resin containing novolac-type recurring units formed by the condensation of a phenolic component of formulaI(two of R<1>s are H and the other is alkyl, aryl, OH, etc.; R is H, alkyl, halogen or OH) and an aldehyde component of formula II(R<2> is H, CH3, etc.), and its amount is 30-150pts.wt. per 100pts.wt. of the component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a curable resin composition having excellent heat resistance properties, mechanical properties, and S flammability.

More specifically, it consists of a curable resin, a substantially linear high molecular weight novolac-type substituted phenolic resin flame release agent, and optionally an inorganic filler, and is cured with significantly improved heat resistance, mechanical properties, and flame retardancy! l! II relates to fat compositions.

Various epoxy resins, urethane resins, urea resins, Mela Z
Cured resins such as phenolic resins and phenolic resins are usually mixed with a curing agent and, if necessary, an inorganic filler and a flame retardant. ing. However, although all of these cured m-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.

The heat resistance properties, mechanical properties,
In order to improve other properties, many cured aim fat compositions containing resol phenolic resins or novolac 31 phenolic resins have been proposed. For example, when the cured MIM resin is an epoxy resin, % of the epoxy resin is mixed with a novolac type phenolic resin.
II fat composition is disclosed in Japanese Patent Publication No. 32-9246, No. 38
-11827 Publication, Publication No. 39-3574, Publication No. 39
-27769 Publication, Publication No. 41-1352, Publication No. 45
-30351 publication, 46-38030 publication, 4
No. 8-8278, No. 48-44958, No. 5
No. 0-19319, No. 51-20537, No. 51-21679, No. 51-21869,
JP 51-24399, JP 51-43403, 1jJ52-3828, JP 52-9480, JP 48-72293, JP 49-1187
Publication No. 97, Publication No. 49-118798, Publication No. 50-7
No. 0497, No. 50-108400, No. 51
-132267 publication, 52-138599 publication,
It has been proposed in Japanese Patent No. 52-144099, Japanese Patent No. 55-29532, etc. However, the novolac type phenolic resins blended into the epoxy resin composites proposed in any of these known documents are all novolac type phenolic resins manufactured by ordinary methods, and their number average molecular weights are is a relatively low molecular weight novolac 21 phenolic resin having a molecular weight of at most 1200 or less, usually 1000 or less. Such relatively low molecular weight Novo2
Even if Tsukuya phenol resin is blended, the resulting epoxy resin composition will have a high thermal deformation temperature, thermal deformation at high temperatures,
Heat resistance properties such as bending strength, mechanical strength, and dimensional stability as well as mechanical properties cannot be sufficiently improved. Moreover, it is of course not sufficient in terms of flammability. Similarly, when the curable resin is a curable resin other than epoxy resin, such as urethane resin, urea resin, melamine am, or phenol 11j1, novolak 11, which has a relatively low molecular weight, can be used.
Even if phenolic resin is used, it is not possible to sufficiently improve the heat resistance properties and mechanical properties of the cured resin composition.
! do not have.

The present applicants have discovered a new polymer, a substantially linear high molecular weight novolak type substituted phenol resin which has a difunctional phenolic component as its main component, and further developed this high molecular weight novolac type substituted 7-functional phenolic resin. A cured resin composition obtained by blending a resin with various cured M and I# resins such as epoxy resins is a cured resin obtained by curing the above-mentioned curable resin alone, and a conventional low molecular weight novolak in the cured layer resin. It was discovered that the heat resistance and mechanical properties were significantly improved compared to any of the curable resin compositions prepared by blending and curing phenolic resin, and the patent application No. 15914/1983 was published.
No. 0, Patent Application No. 1983-73754, Patent Application No. 1983-757
No. 56 and Japanese Patent Application No. 55-73757. The cured resin composition proposed by the present applicant has excellent heat resistance properties and 4i1 mechanical properties as described above, but it is also used in various molded parts for electrical appliances, various industrial molding materials, In applications in fields where strict flammability is required, such as compositions for coatings such as electrical insulation sources, flame retardance has sometimes been insufficient.

The present inventors have investigated methods for improving the flame retardancy of a curable resin composition containing a cured maw such as an epoxy resin, urethane resin, or phenol resin without impairing the heat resistance and mechanical properties. , a curable resin, a substantially linear high-molecular weight substituted phenolic resin having a number average molecular weight (Ms) of 1500 or more, a flame retardant, and a necessary!
! According to Mr. W14, who arrived at the present invention by discovering that a curable composition containing other compounding agents such as an inorganic filler can sufficiently achieve the above object, the curable composition of the present invention The mold resin composition has excellent heat resistance properties such as heat distortion temperature, heat distortion at high temperatures, bend strength, mechanical strength, and dimensional stability, as well as mechanical properties, and has excellent flame retardancy. are doing. Furthermore, the cured layer resin composition of the present invention has significantly higher heat resistance and mechanical properties than a cured resin composition containing a conventional low molecular weight novolac phenolic resin instead of the high molecular weight novolac substituted phenolic resin. Furthermore, the heat resistance properties and mechanical properties are significantly superior to those of a curable resin composition that does not contain the high-molecular-weight Norac-substituted phenol resin. Therefore, the cured ffi resin composition IIB of the present invention can be effectively used in fields such as molding materials and coating materials that require heat resistance, mechanical properties, and flame retardancy.

That is, the present invention uses (A) a cured Ms fat, (b) a bifunctional phenol component as a constituent phenol component, and a high molecular weight novolac type having a number average molecular weight (M1 of 1500 or more and substantially linear). This is a cured WII fat composition containing a substituted phenolic resin and 0 flame retardant.

The curable resin (a) to be blended into the curable resin composition of the present invention includes a curable resin that is cured with a curing agent and, if necessary, a curing accelerator, and a curable resin that is cured by heat. . More specifically, epoxy resins, various urethane resins, urea resins, melamine resins,
Examples include polybismaleyl resin, common novolac 11 phenolic resin, and common resol type phenolic resin. Among these cured maw), it is preferable to apply the present invention to a cured resin that can be cured with a phenolic hydroxyl group-containing compound because the heat resistance and mechanical properties of the resulting cured resin composition are further improved. More specifically, among these curable resins (a), when epoxy resin, urethane resin 11, normal novolak phenol resin, and normal resol type phenol resin are used, a cured maw composition with further improved performance can be obtained. This is preferable because it provides the following. 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 cured resins (A), epoxy 111i1 and urethane 1111 will be more specifically exemplified.

When the curable resin (a) 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 F, 1,1,
2. Glycidyl ether type epoxy resin of poly7 enol compounds such as 2-tetrakis (4-human E1m?siphenylene ethane); Glycidyl ether type epoxy resin of nuclear hydrides of the polyphenol compounds; catechol, resorcinol, hydroquinone, Glycidyl ether-based epoxy resin of polyhydric phenols such as phloroglucin; ethylene glycol, butanediol, glycero~°
Glycidyl ether type epoxy resins of polyhydric alcohols such as alcohol, erythritol, and polyoxyalkylene glycol; Novolak type epoxy resins; Alicyclic type epoxy resins such as vinyl cyclohexane dioxide, limonene dioxide, and dicyclopentadiene dioxide; Examples include polyglycidyl ester-based epoxy resins of ester condensates of polycarboxylic acids such as 7-talic acid and cyclohexane-1,2-dicarboxylic acid; polyglycidylamine-based epoxy resins; and methylevikcho epoxy resins.

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

Epoxy resin composition K containing these epoxy resins
Ij! ? As the curing agent blended according to 11, any compound generally known as a curing agent for epoxy resins can be used. Specifically, examples include chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, diethylenepentamine, dipropylene diamine, and diethylaminoprobylamine; cycloaliphatic polyamines; aliphatic boriaones. Adduct; Ketoimine; Modified aliphatic polyamine; Polyamidoamine; Aromatic amine; Aromatic modified amine; Aromatic modified polyamine; Tertiary amine curing agent; Mercaptan curing agent; Acid anhydride curing agent; Copolymers with acid anhydride groups such as ethylene-maleic anhydride copolymers; Compounds with phenolic hydroxyl groups such as Novolak 11 or epoxy resin initial metals; Dicyandiamide; Compounds such as melamine. can be given.

In addition, when the cured resin (b) blended into the cured layer resin composition of the present invention is a urethane resin, the urethane resin may be selected from polyinocyanate, polyethyl polyol, polyester polyol, or other polyol compounds. Either a resin with urethane bonds formed or a resin with urethane bonds formed from a urethane prepolymer and a curing agent can be used.

Specifically, the polyisocyanate constituting the polyurethane resin includes hexamethylene diisocyanate, chloride diisocyanate, 1-methyl-2,4
-Diisocyanate, cyclohexane phenylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane-4,4'-
Diincyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4',4''-triisocyanate, xylylene-2,2'-diisocyanate, improvilbenzene-2,4-diisocyanate,
An addition product of 1 mole of trimethylolpropane and 3 moles of tolylene diincyanate, and a high molecular weight polyincyanate obtained by polymerization of the polyinsyanate are used.

The polyol compound constituting the polyurethane resin is a compound having two or more hydroxyl groups in one molecule, and specifically includes polyethylene glycol, dipropylene glycol in polyol, poly(oxyethylene,
Polyether polyols such as oxypropylene glycol; hydrolysates of copolymers of α-olefins and unsaturated organic carboxylic esters; polyesters with terminal hydroxyl groups produced from polybasic acids and glycols Polyol: Acrylic polyol; Castor oil derivative polyol, tall oil derivative polyol; Polytwo containing hydroxyl groups at both ends of a copolymer such as butadiene, styrene, butadiene-acrylonitrile;
Epoxy containing a sil group in hydro*N1 A modified product of a hydroxyl group-containing V epoxy resin; examples include hydroxyl compounds such as a compound containing a sil group in a hydro compound obtained by reacting a polyisocyanate with an excess of a polyol compound.

It is a compound A containing two or more incyanate groups in one molecule, which is obtained by reacting the urethane prepolyt ff-t2, ytt triol compound constituting the polyurethane resin with an excess of polyinsyanate.

Furthermore, as a curing agent that is necessarily added to a resin composition having one urethane bond according to the IK, the curing agent is generally
f! A remer hardener can be used. Specifically, for example, one or more compounds of polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, fluoropylenediamine, tetramethylenediamine, hexamethylenedi7one, or the above-mentioned compounds. Polyolization of 4
One or more compounds of F411F are used.

The high molecular weight novolak substituted phenol resin (b) blended into the cured m* fat composition of the present invention mainly contains bifunctional phenol 111 as a constituent phenolic component, and has a number average molecular weight [N,N-dimethylacetamide solvent It is a substantially linear high molecular weight novolak-substituted phenol resin which has a value (Ns) J of 1500 or more as measured by vapor pressure osmotic pressure method.

In the present invention, the high molecular weight novolac-substituted phenol resin (4 <hereinafter sometimes simply referred to as high molecular weight novolac ffi resin) as a compounding component is a new polymer,
It may consist entirely of substantially linear novolac repeating units, or it may have a number average molecular weight of 250 to 1200.
Chain extending groups consisting of divalent hydrocarbon groups are alternately added to each block of novolac repeating units at a ratio of 0.5 to less than 1 mole and <KO, 6 to less than 1 mole per 221 moles of the pro-221. It may also be a high molecular weight novolak-substituted phenolic resin. The important thing is this high molecular weight novolac! ! ! The resin is substantially linear and has a density of 1500 or more,
Preferably in the range of 1.700 to 15,000, and <
KE - 2.000 or i o o, o o
It has a number average molecular weight [1%] in the range of o.

Here, the number average molecular weight (NsJ is N.

This is a value measured by vapor pressure osmosis method in N-dimethylacetamide solvent. Also, here, "substantially linear" means
It means that the polymer chain has a linear structure having a linear or branched structure, and it means that it does not contain a network structure (that is, it does not contain gelatinized material J).

The high molecular weight novolac 1718! The number average molecular weight of II@ is in the range of <1500 or more as described above;
When the number average molecular weight of the resin becomes large, the hardened resin JIIK
When blended, it is preferable because a composition with excellent heat resistance, mechanical properties, and flammability can be obtained. Moreover, the molecular weight distribution of the high molecular weight novolac lid 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, which is favorable! <KtFf is 60 weight or more, and <KtFf is 70 weight or more. Further, the molecular weight distribution expressed as the ratio of weight average molecular weight (Afw) to number average molecular weight (1%) K (!/M1) is preferably 1.
The range is from 8 to 20, particularly preferably from 2 to 10. Further, the melting point of the high molecular weight novolak type resin is usually in the range of 120°C or higher, preferably 150°C or higher.

The high molecular weight Novoc! More specifically, as the novolac repeating unit constituting the jI11 fat@, (1) the phenol component constituting it has the general formula [1,11 (wherein two of the three R1 is a hydrogen atom, and the remaining one is an alkyl group having 1 to 8 carbon atoms, and the remaining one is an alkyl group having 6 carbon atoms.
"7 to 10 aryl group, halogen atom or hydroxyl group, preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group, ethyl group, isopro, pyru group, especially -butyl group, -detopyl group and octyl group;
Particularly preferred is a 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 hydrogen atom, and a hydroxyl group, and preferably one of the two R's is It is a hydrogen atom, and the remaining one represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and particularly preferably both R represent a hydrogen atom. ] at least 11
The difunctional phenolic component of 1 is in the range of 70 to 10"0 mol, preferably 80 to 100 mol, particularly preferably 90 to 100 mol, and the trifunctional phenolic component is in the range of 70 to 10"0 mol, particularly preferably 90 to 100 mol. , preferably from 0 to 20 mol, particularly preferably from 0 to 10 mol (provided that the total of both phenolic components is 100 mol). The aldehyde component constituting (it) has the general formula [II, IR”
-CHO [n) (wherein, R3 represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and an I-logonated methyl group,
Preferably, it is at least one aldehyde component represented by a hydrogen atom or a methyl group, and <R6 or a hydrogen atom.

In this novolak type repeating unit, the bifunctional phenolic component is a hydroxyarylene unit represented by the general formula (III) (wherein R1 and R each represent the same group as above) in the wrinkled resin molecule. At the molecular terminal of the polymer, a compound of the general formula [IV] (wherein R1 and R represent the above-mentioned groups, respectively) exists as a diaryl unit in the middle. The trifunctional phenol component of the resin component also exists as a hydroxyarylene unit in the resin molecule, similar to the above general formula [1M], and at the molecular end of the resin, a hydroxyaryl unit exists as in the above general formula [IV]. Exists as a unit.

Further, the aldehyde component constituting the high molecular weight novolac type resin has the general formula (VJ It is present as an alkylidene unit represented by F.The structure of the novolac type repeating unit is a chain structure in which the hydroxyarylene units and the alkylidene units are alternately arranged. It is.

More specifically, the structure of the high molecular weight novolac resin is such that when the constituent phenol component is only a bifunctional phenol component represented by the above general formula [l], the resin has a linear structure. When the content of the trifunctional phenol component increases, the chain may become branched. The ratio of the aldehyde component to all the 7-functional alcohol components constituting the high molecular weight novolac resin is usually 0.90 to 1.0 mol, preferably 0.95' to 1 mol of all 7-functional alcohol components. Ik is in the range of 1.0 mol. The high molecular weight novolac maw usually does not contain a methylol group, but it contains 0.0 methylol groups per 1 mole of total heptanol aUC.
There is no problem even if it contains a trace amount of methylol group, which is less than 14%.

Among the phenolic components constituting the high molecular weight novolak resin), the difunctional phenolic component is represented by the general formula [IJ], and has two active hydrogen atoms on the benzene nucleus for a substitution reaction. It is a phenol having an atom,
Specifically, phenols having an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, /% Ei or a hydroxyl group in the ortho or para position relative to the hydroxyl group in the general formula [1] above. It is. More specifically, the following examples of ortho isomers and para isomers of phenols can be produced. However, cresol, ethylphenol, duck-globylphenol, inoflovirphenol, %-butylphenol, m-butylphenol, g-detopylphenol, dai-amylphenol, tart-amylphenol, hexylphenol, heptylphenol, octylphenol Alkylphenols such as; halogenated phenols such as chlorophenol, chlorophenol, and fromophenol; and arylphenols such as phenylphenol and tolylphenol. Further, as the bifunctional phenol component represented by the general formula [13], 2,6-xylenol, 3,4-xylenol, 2.
5-17 lenol, 2,6-diethylphenol, 6.
4-diethylphenol, 2.5-diethylphenol, 2.3-diisopropylphenol, 3,4-diisopropylphenol, 2.5-diimpropylphenol, 2g5-dichlorophenol, 6゜4-dichlorophenol, 2.5- Diclomitzenol, 2-methyl-
6-7 alephenol, -rifuro 3-methyl-4-phenylphenol, 2-methyl-5
-7 ale phenol can be exemplified. The trifunctional phenol component constituting the bulk molecular weight novolac-substituted phenol resin is at least 1 m of the phenolic components, and may be a mixture of two or more.

The trifunctional phenol JIIIE component constituting the novolac repeating unit of the high molecular weight novolac Taki resin (b) is:
It is a phenol having three active hydrogen atoms on the benzene nucleus for substitution reactions, and specifically includes phenol, meta-substituted phenol, and 3,5-substituted phenol. These trifunctional phenols are in the meta or 3
, the substituent at the 5-position includes an alkyl group, /
% rogen or hydroxyl group. Among these trifunctional phenols, preferred trifunctional phenols have the general formula (wherein R is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen group, and a hydroxyl group). The phenols represent the same or different substituents.] More specifically, phenol, lin-cresol, dashi-ethylphenol, lin-su-furobylphenol, shu-inoflovirphenol, 5 -s-7'?rufenol, 1-phthylphenol, 1e-detoptylphenol, 1-amylphenol, 1-gami-kiri-
amylphenol, non-1-butamylphenol, lin-hexylphenol, nawate-hebutylphenol, m-
Octylphenol, bait-fluoropheno-A/s s
Meta-substituted phenols such as -/lolophenol, sac-furo47m-/-l, and resorcinol; 3.5-xylenol, 3.5-diethylphenol, 6,5-diisopropylphenol, 3゜5-di-bonito-butyl phenol,
3.5-di-vg-phthylphenol, 5*5-
') w-7iruphenol, 3,5-diC-detoamylphenol, 3゜5-diethylphenol, 5.5-diethylphenol, 3,5-dioctylphenol, 3
Examples include 3.5-disubstituted phenols such as 5-di:ya lophenol, 3.5-dichlorophenol, 3.5-dibromophenol, and 3.5-dirodphenol. Furthermore, among these difunctional phenolic components, in the general formula [VI], 2
It is preferable that one of the two R's is a hydrogen atom and the other one is a phenol component represented by a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or chlorine; one of which is a hydrogen atom and the other one is a hydrogen atom, a methyl group, an isoptapyru group, a flag-methyl group, 1e
Particularly preferred is a phenol gli component represented by an ft-butyl group or an octyl group.

The aldehyde component constituting the novolac repeating unit is an aldehyde component represented by the general formula [fi]. Specific examples of these aldehyde components include formaldehyde, acetaldehyde, monochloroacetaldehyde, dichloroacetaldehyde, and tricloacetaldehyde. Among these aldehyde components, formaldehyde or acetaldehyde are preferred, and formaldehyde and K are preferred. These aldehyde components exist as alkylidene groups represented by the general formula [■] in the wrinkled high molecular weight novolak substituted phenol resin.

The high molecular weight novolac layer resin 0 blended into the cured m* fat composition of the present invention may consist only of the novolac repeating unit consisting of the phenol component unit and the aldehyde component unit as described above, and further As mentioned above, each block of novolac repeating units (-) with a number average molecular weight [NsJ usually in the range of 250 to 1200 is a chain length group or 11-linked group (hereinafter referred to as
#Sometimes called an extender component unit. ) may be formed alternately.

To be more specific regarding the structure of the substantially linear high molecular weight novolac-type resin 0, this type of resin has a relatively low molecular weight and substantially linear novolac-type repeating unit block (, ) and a chain extender component. It is composed of units (&), and the novolak type repeating unit block (s
) and chain lengthening agent component units (&) are alternately arranged and connected to have a high molecular weight, and the molecular weight is 1.
The difference between KII and 4I is that 1111Kl [novolak-type repeating unit block] is attached. Among this type of high molecular weight novolac type **, the molecular structure is the simplest in 1 to 41. Two molecules of the chain novolac repeating unit block (,) are connected by one molecule of the chain extender component unit (&) K. This is a resin in which five molecules of the novolac repeating unit (6) and two molecules of the chain extender component unit (&) are alternately arranged and connected, and then four molecules of the novolac repeating unit are connected. A resin in which the unit block (a) and three molecules of the chain extender component units (&) are alternately arranged and connected, and similarly, one molecule of the Isanovolac Otori repeating unit block -) and (%-1) molecules of the A resin in which chain extender component units (groups) are alternately arranged and connected can be exemplified.

The high molecular weight novolak ms fat blended into the cured resin composition of the present invention is schematically represented by substantially the general formula [■] Z+Y, -Z9 Y, -2 represents a block of substantially linear novolac repeating units formed by condensation of a class component with the aldehyde component, Y represents a chain extender component unit consisting of a divalent hydrocarbon group, and p represents at or Indicates an integer of 1, and 悌 indicates 0 or a number greater than or equal to 1.It is expressed as having a polymer chain represented by p is 1 when the unit blocks are alternately bonded, and p is 0 when it consists only of the novolak repeating units and does not substantially (apparently) contain chain extender component units. .

The high molecular weight novolak 'Milli! As mentioned above, the chain extender component unit (#extending group or bridging group) constituting 1cB3 is a divalent hydrocarbon group, and furthermore, it is a hydrocarbon group having 1 to 16 carbon atoms, and more specifically, is an alkylidene group, an alkylene group, a cycloalkylev group, a cycloalkylidene group, an arylalkyritene group, an arylalkylene group, an arylenebisalkylene group C-R"
-Aday R4-]. Examples of the alkylidene group include a methylene group, ethylidene group, glopylidene group, butylidene group, and pentylidene group. Specific examples of the alkylene group include ethylene group, propylene group, isopropylene group, butylene group, pentyline group, and hexylene group. Specific examples of the cycloalkylev group include a cyclopentylene group, a cyclohexylene group, and a methylcyclohexylene group. Specific examples of the cycloalkyritene group include a cyclopentylidene group, a cycloachiritene group, and a methylcyclohexylidene group. Specific examples of the arylalkyritene group include benzylidene group, .-xylidene group, so-xylidene group, and p-xylidene group. Specific examples of the arylalkylene group include styrene group, α-methylstyrene group, and p-methylstyrene group. Specific examples of the arylene bisalkylene group include an 0-xylylene group, a -xylylene group, and a she-xylylene group.

Among these chain extender component units (b), an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, an arylalkylidene group, an arylalkylene group, or an arylene bisalkylylene group are preferable. , especially alkylidene groups having 1 to 4 carbon atoms, alkylev groups having 2 to 5 carbon atoms, 7 to 9 carbon atoms
An aryl alkylidene group, an aryl alkylene group having 8 to 10 longitudinal primes, or a 7-arylene bisalkaline group having 8 to 10 carbon atoms is preferable, and the molecular weight of these chain extender component units (i) If it becomes too large, the melting point of the produced high molecular weight novolak type substituted phenol resin will decrease and the flexibility will increase.
Even if this resin is used as a cured 1111RN compounding agent, it is difficult to obtain a cured layer resin composition with excellent heat resistance and mechanical properties. Therefore, these chain extender component units (
The molecular weight of &) is usually 14 to 200, preferably 1
It ranges from 4 to 170.

The high molecular weight novolak resin CA) 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) (General formula El) (In the formula, two of the three R1 are hydrogen atoms, and the remaining one is an alkyl group having 1 to 8 carbon atoms, and 6 carbon atoms.
to 10 aryl groups, halogen atoms, or hydroxyl groups, and R is the same or different group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 vertical primes, a halogen atom, and a hydroxyl group. Phenols mainly composed of at least one type of difunctional phenol, or 01) A phenol component mainly composed of the above difunctional phenols and the general formula [formerly R1-ctro [13 (in the formula, R3 is a hydrogen atom, It represents one type of substituent selected from the group consisting of a methyl group and a halogenated methyl group. ) (1) Dimethylolated products of difunctional and trifunctional phenols; When the chain extender selected from the group consisting of certain resol-type substituted phenolic resins, (liD aldehydes, 4V) ketones, 0 diols, and 4/-cybarides (wherein the reactants) is in the phenols, The chain extender (c) is a resol-type substituted phenol resin (II). ] in the presence of an acidic catalyst in such a manner that the difunctional phenol accounts for at least 70 moles of the 7-functional phenol component in the final novolac-substituted phenolic resin, and in an N,N-dimethylacetamide solvent. It is produced by condensing until the number average molecular weight of the final novolac-substituted phenol resin reaches a range of 1500 or more as measured by pressure osmosis method.

The blending ratio of the substantially linear high molecular weight novolac substituted phenol resin to be blended into the cured m* resin composition of the present invention is usually 101 parts by weight per ml of the cured resin.
It is particularly preferable to incorporate 30 to 150 parts by weight of lliWM because the heat resistance and KIIA mechanical properties of the cured resin composition are improved.

The flame retardant 0 to be blended into the cured layer composition of the present invention is specifically an organic halogen compound (phosphorus-containing compound). ), boron bulk compounds (excluding hydroxides and carbonates), phosphorus and phosphorus compounds, antimony compounds, heptagonal compounds, bismuth compounds, hydroxides of metals of groups 1III and 16 of the periodic table, or It is at least one selected from the group consisting of podates, and two or more of these may also be used together. Among these flame retardants, use of a flame retardant selected from the group consisting of organic halogen compounds, phosphorus and phosphorus compounds, and combinations of these and antimony compounds results in a hardening composition with further improved flame retardant effect. It is preferable to blend a flame release agent consisting of an organic compound and an antimony compound.

The combination side of these flame retardants 0↓ is the cured ff1ll fat (
A) and the above-mentioned high molecular weight novolac resin 00 in a total amount of 100 parts by weight, usually in a range of 2 to 60 parts by weight.

Among the flame release agents 0, organic halogen compounds (excluding phosphorus-containing compounds) include 1゜2-dichloroethane, 1,2-diproethane, 1゜1.2.2-tetrachloroethane, 1,1 ,2゜2-tetrabromoethane,
Aliphatic halogens such as hexachloroethane, hexabromoethane, dibromotetrafluoroethane, 1,2,3.4-tetrachlorobutane, 1゜2.3.4-tetrachlorobutane, chlorinated buffin, brominated paratwin, etc. Compound 11; Bentapumo monochlorocyclohequinane, hexapromocyclohequinane, hexapromocyclohequinane, hexachlorocyclohexane, hexabromocyclodecane, hexabromocyclodecane, hexachlorocyclopentadiene, hexabromocyclopentadiene, chlorendo acid, diallyl chlorendo acid , -hydrochlorendoic acid, similar iodine compounds, etc. / compound 411j; hequinapromopenyan,
11? Su10 lobenzene, pentabromomethylbenzene, pentafluoromethylbenzene, hexapromodiphenyl, aP sachlorodiphenyl, hema submoji7 ether, hexachlorodiphenylny? dibromocresyl glycicyl ether, decabromo biphenyl ether, decachlorobiphenyl ether, decaboomodiphenyl oxide, decachlorodiphenyl oxide, octabromodiphenyl ether, octachlorodiphenyl ether, tribromophenol, trichromitzenol, tetrabromobisphenol A1 tetrac o a his 7 enr A1 tetrabromobisphenol F1 tetofpromobisphenol AD, dibromodichlorobisphenol A1 diacetate of tetrabromobisphenol A, tetrachlorobisphenonyl A
diacetate, tetrabromo-2,2-bis(4,4
'-diphenyl λ propane in dimeth, tetrachloro-2
, 2-bis(4,4'-dimeth, sifcinylnopropane, tetrabromo phthalic anhydride, tetrachloroheptalic anhydride, chlorinated epoxy phenolic resin,
Examples include aromatic halogen compounds such as odorized epoxy novolaks, phenolic resins, brominated bisphenol A'll epoxy resins, and similar iodine compounds.

Among these organic metal halides, aromatic halogen compounds are preferably blended because a cured resin composition with excellent flame retardation properties can be obtained. In addition, among these organic halogen compounds, it is preferable to incorporate an organic chlorine compound or an organic bromine compound because it creates a curable resin composition with excellent flammability. ,stomach. Additionally, these organic halogen compounds can be used alone as flame release agents, but they can also be used in combination with other flame retardants. For example, it is preferable to use these organic halogen compounds and the antimony compound described below, especially antimony trioxide, in combination because a synergistic effect is obtained on flame retardancy. The atomic ratio of the antimony atom of the metal antimonide to the halogen atom of the compound is usually 0.
It ranges from 5 to 5, preferably from 0.7 to 2.

- When the organic metal halide is used as a fuel, the blending ratio is 100% by total weight of the hardened MS fat) and the high molecular weight novolac MS fat).
Usually 1 to 20 parts by weight of No.p Ken atoms
parts by weight, preferably in the range from 2 to 10 parts by weight.

Among the JIIIA agents 0, examples of boron compounds (excluding hydroxides and carbonates) include lead borate, borax, and barium metaborate. When using the boronated metal as the flame retardant 0, the blending ratio should be as follows:
and the above-mentioned high molecular weight novolak m resin) total weight 1
Usually 1 to 15 boron atoms per 00 parts by weight
parts by weight, preferably in the range of 2 to 8 parts by weight.

Among the flame release agents 0, phosphorus and phosphorus compounds include simple phosphorus such as red phosphorus and yellow phosphorus; trimethyl phosphate, triethyl phosphate, triisoglobyl phosphate, tributyl phosphate, trihexyl phosphate, and Phosphate esters such as octyl phosphate, tryptoxycotyl 7ate, triphenyl phosphate, tricresyl phosphate, talesyl diphenyl phosphate, octyldiphenyl phosphate; tris (β-chloroethyl) phosphate, tris (β-bromoethyl J phosphate, Tris(dichloropropyrne phosphate, tris(dibromoglopyr) phosphate, tris(furo-heptaglopyr lambda phosphate, tris(chloropropyr diphosphate, tris(dipromoglopyr) phosphate,
Halogen-containing phosphate esters such as bis(2,3-dipromoglovir] mono(2,3-dichloroglobyrne phosphate, tris(2,6-diptetramopropyrne phos7ate), bis(chloroproviran monoocterphosphate); Polyphosphoric acid esters such as phosphonates, polyphosphates, aromatic polyphosphates, and epoxy-containing phosphonates; phosphonate-based polyols, phosphatide)
[Polyphosphate polyols such as polyols can be exemplified. Among these phosphorus compounds or phosphorus compounds, it is preferable to blend a phosphoric acid ester, a polyphosphoric acid ester, or a polyphosphoric acid polyol because a cured resin composition having excellent flame retardancy can be obtained. Moreover, although these phosphorus or phosphorus compounds can be used alone as flame retardant 0, they can also be used in combination with other flame retardants. For example, when the phosphorus or phosphorus compound is a phosphoric acid ester that does not contain a halogen atom, it is preferable to use the organic halogen compound and the phosphorus or the phosphorus compound together because a synergistic effect on flame retardancy can be obtained. At that time, the blending ratio of both in the cured layer composition is usually 0.5 to 5, preferably 0.5 to 5, as the atomic ratio of the halogen atom of the organic/S halogen compound to the phosphorus atom of the phosphorus or phosphorus compound.
．． It ranges from 7 to 2.

When the phosphorus or phosphorus compound is used as the flame release agent 0, the blending ratio thereof is usually 1 to 20 parts by weight as phosphorus atoms per 100 parts by weight of the total weight of the cured layer resin) and the high molecular weight novolak Kei resin 00. Department,
Preferably it is in the range of 2 to 10 parts by weight.

Among the above-mentioned fuel agents 0, specific examples of antimony compounds include antimony trioxide, sodium antiheptinate, trimethylstibine, triethylstibine, triphenylstibine, and the like. Also, flame retardant 0
When these antimony compounds are used, the blending ratio is 1 to 1 of the curable resin (A) and the high molecular weight novolac Gekiju! The amount of antimony atoms is usually 1 to 15 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the total weight of @.

Examples of the arsenic compound or bismuth compound among the flame release agents 0 include arsenic trioxide, bismuth sanburoka, trimethylarsine, triethylarsine, triphenylarsine, and the like.

In addition, when these arsenic compounds or bismuth compounds are used as flame retardant 0, the blending ratio thereof is as follows: arsenic atoms or Usually 1 to 15 parts by weight, preferably 2 parts by weight as bismuth atoms
and 8 parts by weight.

In addition, among the flame retardants 0, specific examples of hydroxides or carbonates of metals in Group 16 of the periodic table and in Group 1,
Examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, boric acid, magnesium hydroxide, calcium carbonate, strontium carbonate, barium carbonate, and basic aluminum carbonate. When hydroxides and carbonates of these metals are used as the flame retardant, their blending ratio is determined based on the total weight of 100 parts by weight of the cured resin) and the high molecular weight novolac MS resin. Usually 1 as a metal atom of Group H or Group H of the table
from 2 to 20 parts by weight, preferably from 2 to 10 parts by weight of I
It is i8.

The filler that may be added to the cured m* fat composition of the present invention as required is an inorganic filler. Specifically, inorganic fillers include silica, silica/alumina, alumina, glass powder, glass beads, glass fiber, asbestos, mica,
Graphite, carbon delicacy, titanium oxide, molybdenum disulfide, beryllium oxide, oxidation! Examples include magnesium, calcium oxide, magnesium hydroxide, calcium hydroxide, talc, metal powder, metal fiber, and the like. Heat resistance and mechanical properties are improved no matter which of these inorganic fillers is blended. Among these inorganic fillers, blending glass fiber, carbon fiber, asbestos, etc. further improves mechanical strength such as impact strength and compressive strength, while blending graphite, titanium oxide, molybdenum disulfide, etc. improves wear resistance. is further improved, arc resistance is greatly improved by adding mica, multispaste, glass powder, etc., and electrical properties such as conductivity are improved by adding carbon black, metal fiber, metal powder, graphite, etc. Combining alumina, titanium oxide, beryllium oxide, etc. improves thermal conductivity. The blending ratio of these inorganic fillers is determined by the curing Wl#I! blended into the curable resin composition. Cured IMIII fat 10
The amount is usually 10 to 250 parts by weight, preferably 30 to 200 parts by weight, and particularly preferably 60 to 150 parts by weight, based on 0 weight ISK.

The cured MS fat composition of the present invention includes the above-mentioned cured INR fat (b), the above-mentioned substantially coat-like high molecular weight novolac AM fat (0), the above-mentioned flame retardant (0), and optionally the above-mentioned inorganic filler. Furthermore, appropriate amount of compounding agents are added as necessary. For example, if the cured ant fat is a resin that can be cured with a hardening agent, a hardening agent, a hardening accelerator, a heat stabilizer, an antioxidant, a lubricant, a filler other than the inorganic filler suitable for the hardening resin, and a filler other than the inorganic filler. Agents are added as necessary. Among these compounding agents, as curing agent KII, the high molecular weight novolac type resin, which is an essential component of the cured resin composition of the present invention, can serve as a curing agent for the cured MS resin (a). In case, a curing agent other than the high molecular weight novolak is required! !
Meals can be distributed accordingly. In addition, if the high molecular weight novolac resin 0 cannot be used as a curing agent for the cured layer resin, the above-mentioned curing agent is usually blended. These must-haves! The various compounding agents to be blended depending on the type of cured resin and the use of the composition vary, and conventionally known compounding agents can be used. Further, the proportions of the various compounding agents blended in accordance with these requirements also 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 has excellent heat resistance and mechanical properties such as heat distortion temperature, heat distortion at high temperatures, bending strength, mechanical strength, and dimensional stability, and is also flame retardant. It has outstanding characteristics.

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

The reference example is a linear low molecular weight novo 2/11 obtained by a normal method.
jp-cresol/indicative aldehyde)'1M11 (M%
:51CN100f, 2.6-dimethylo, -p-cresol 31.1F, 60% nitrate #0.28-, o-dichlorobenzene 10011/ were placed in a reactor and reacted at 175°C for 4 hours with stirring. .

The reaction mixture was poured into methanol 1j to remove unreacted materials, and then dried to obtain resin 12 (1 (@ ratio 97-n).

Vapor pressure osmotic pressure method (in dimethylacetamide, 90°C) K
The number average molecular weight M% of this resin was 5550, and the molecular weight distribution (Rw/TIs) of this resin was measured by gel permeator chromatography.
was 6.2.

The melting point of this resin was determined to be 300° C. or higher using a microscopy method.

Table 1 shows the characteristic values of the 1B nuclear magnetic resonance spectrum measured by dissolving this resin in pyridine-ds. From this result, the methylene proton of the methylol group with a τ value of around 53 is not observed, which indicates that it does not contain a terminal K) tyrol group. - Novo2 flip-cresol with a linear structure in which cresol units and methylene units are arranged alternately.
It was confirmed that it was formaldehyde resin. Furthermore, it was confirmed that this resin had a three-dimensional crosslinked structure (no gelled product J) because it was completely dissolved in dimethylacetamide.

Table 1 Reference Example 2-4 In Reference Example 1, the low molecular weight novolac flip-cresol formaldehyde resin (Reference Example 2), which is listed in Table 2, was used instead of the tentative molecular weight novolac flip-cresol formaldehyde resin (reference example 2). ! ! ! ? -t-
Reference Example 1 except that detoptylphenol/formaldehyde resin (Reference Example 6) and novolac flip-chlorophenol/formaldehyde resin MC Reference Example 4) were used.
I went in the same way.

In addition, the number average molecular weight (R
The structures of s) and @fat were confirmed by the same method as in Reference Example 1. It was confirmed that all the resins obtained by these methods were novolac-type substituted phenol/formaldehyde resins with a linear structure in which phenol component units and methylene units were arranged alternately, as in Reference Example 1. . Furthermore, since all of these resins were completely dissolved in dimethylacetamide, it was confirmed that there was no three-dimensional crosslinked structure (gelled product). The properties of these resins are shown in Table 2.

Reference Examples 5 to 6 In Reference Example 1, the novolac fi1m-cresol/p-cresol/formaldehyde cocondensation resin shown in Table 3 was used in 5 instead of the raw material novolac type p-cresol/formaldehyde resin, and the rest other than 9 were for reference. Do the same thing as Example 1. The structure of the resulting resin was confirmed by the same method as in Reference Example 1 above.

The number average molecule of this resin (1kCM%) was measured by vapor pressure osmotic pressure method (
Molecular weight distribution (Mw/
us) t gel permeability electromagnetography,
One point was measured using microscopy. The composition ratio of p-cresol component units and inert-cresol component units constituting this resin was determined by dissolving this resin in pyridine-DS and measuring it based on the data of the 9H nuclear magnetic resonance spectrum. . The measurement data is shown in Table 6.

In addition, the structures of these resins were confirmed by the same method as in Reference Example 1, and the results showed that among these resins, the resins of Reference Examples 5 and 6 have p-phenol component units and di-phenol component units. A novolac type having a linear structure containing both phenolic component units, in which these phenolic component units and methylene units are arranged alternately, and which is branched in a part of the inertia-phenol component unit and has a necessary branch chain. It was confirmed that it was a substituted phenol/formaldehyde resin. Also, since all of these resins are completely soluble in dimethyl acetate, it can be confirmed that they do not have a three-dimensional crosslinked structure (gelled product). The results obtained are shown in Table 4. Reference Example 7: 9411 (I flLOl ) for phenol, 770 IC (0,861% ol) for 579 and 1 d (0,274 * 1 d of hydrochloric acid) by weight. ) was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, heated and stirred, and the reaction was continued for 4 hours after starting reflux. and j
l-) Add luenesulfonic acid 11 (54swj),
A vacuum dehydration device was attached to the reactor, and while heating under reduced pressure, the temperature of the reactant was increased to 180 mHI at a pressure of 10 μH9.
Perform dehydration and dephenolization until reaching 9. the result,
A brown solid resin 88I (resin yield 84%) was obtained. Jim@L found that the resulting resin was insoluble in N-dimethylacetamide and had a three-dimensional crosslinked structure (gelled product). The remaining 9,074 lbs. of the resin was dissolved in N,N-dimethylacetamide, and it was confirmed that it was a branched novolac type phenol formaldehyde resin. The number average molecular weight (i%) of this branched novolak type phenol-formaldehyde resin determined by the vapor pressure osmotic pressure method was 1090.

Reference example a Phenol 94II (1st 91), 57% formalin 7
0 g (0,86 woJ) i and 1 wt hydrochloric acid 1 d (0,
275ss.j) was placed in a reaction lIK equipped with a thermometer, a stirrer, and a reflux condenser, heated and stirred, and the reaction was continued for 4 hours after starting reflux. Then, p-toluenesulfonic acid 11 (5.3 mmol) yk was added, a vacuum dehydration device was attached to the reactor, and while heating under reduced pressure, the temperature of the reaction product was brought to 180 ■HIi at a pressure of 10wmHI.
After reaching this point, dehydrate and remove phenol for another 30 minutes.9. As a result, a brown solid resin of 709 (resin yield: 67-) was obtained. It was confirmed that 58% of the nine resins obtained were insoluble in N,N-dimethylacetamide, 2S-based, and had a three-dimensional crosslinked structure (gelled product). remaining 42 resin
It was confirmed that the product was a branched novolak type phenol formaldehyde resin dissolved in N,N-dimethylacetamide. This branched novolac type phenol formaldehyde resin had a running number average molecular weight (Mn) of 470 as determined by the vapor pressure osmotic pressure method described above.

Reference example 9゜p-cresol 1081 (1 mol), 70 g (0.86 mJ) of 37% formalin and 1 ml of 1 heavy duty hydrochloric acid
1/(0,274 hours) was placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, heated and stirred, and the reaction was continued for 4 hours after starting reflux.

and? =) Luenesulfonic acid 111 (5,5-)
was added, a vacuum dehydration device was attached to the reactor, and while heating under reduced pressure, the temperature of the reactant was brought to 1 at a pressure of 10 sm HII.
Dehydration and removal of phenol were performed until reaching 80 mHI. As a result, 89 g of brown solid resin (resin yield 75%) was obtained. The nine resins obtained are N.

It was confirmed that it was completely dissolved in N-dimethylacetamide and did not contain a three-dimensional crosslinked structure (gelled product). The molecular structure of this resin was confirmed to be a linear novolak-type phenol formaldehyde resin. The number average molecular weight (R%) of this linear novolac type phenol formaldehyde resin was determined by the vapor pressure osmotic pressure method described above.
70 and 6 90 Reference examples ICL Translocated chain-like low molecular weight Noboguts 1Wi obtained by a normal method
p-cresol formaldehyde resin (Af%=51
0, Mso/M%=1.4, melting point 83°C) 100Lp-
Xylylene glycol 27.6jl.

60-nitric acid 0.2811/, toluene 2701 volume 5
0011/Put in autoclave and stir while stirring 175
Incubate for 4 hours at 9°C. The reaction mixture was poured into methanol 1j to remove unreacted materials, and then dried to obtain resin 729 (
The number average molecular weight of this resin measured by vapor pressure osmometry (in dimethylacetamide, 90°C) was 2000, and the yield of this resin was 2000 as measured by gel-neutral chromatography. The molecular weight distribution (Mv/M%) is 2.5 and 69. In addition, the melting point of this resin was determined by microscopy.The melting point of this resin is 6 at temperatures above 500℃. As a result, the existence of a novolak-type p-cresol formaldehyde resin skeleton was confirmed, and the production of a high molecular weight resin different from the raw material resin revealed that the low molecular weight novolac type p-cresol formaldehyde resin tra-xylylene was produced as a raw material. The polymer reacts with glycol, and the Davolac 1l-p-cresol/formaldehyde resin component units and p-xylene group component units are alternately arranged and connected, resulting in a high molecular weight. It was confirmed that novolac-type p-cresol formaldehyde resin component units were bonded.

Since this resin completely dissolves in dimethylacedoide, tetrahydrofuran, etc., it was confirmed that it does not contain any three-dimensional crosslinked structure (gelled product) and is substantially linear.

Reference Examples 11 to 1a The same procedures as Reference Example 10 were carried out except that the compounds listed in Table 5 were used instead of p-xylylene glycol as the chain extender.

In addition, the number average molecular weight (M
%) and the structure of the resin were confirmed in the same manner as in Reference Example 10. In each of the resin wires produced in this way, the molecular terminal of the raw material novolak-type p-cresol formaldehyde resin reacts with the chain extender, and the novolak-type p-cresol formaldehyde resin component unit and the chain extension shown in Table 5. It was confirmed that the molecular weight was increased by alternately arranging and connecting the agent component units, and that novolac type p-cresol formaldehyde resin component units were bonded to the molecular terminals of the resulting resin. Furthermore, since this resin completely dissolves in dimethylaminoamide, tetrahydrofuran, etc., it was confirmed that it did not contain any three-dimensional crosslinked structure (gelled product) and was substantially linear. The properties of these resins are shown in Table 5.

Reference Examples 19 to 21° In Reference Example 10, Novolak 1Ip-cresol.
Reference Example 10 except that the novolak l1lo-cresol formaldehyde resin, novolak flj, p-te det-butylphenol formaldehyde resin, and novolak type p-chlorophenol formaldehyde resin tl listed in Table 6 were used as the formaldehyde resin. Go like nine. In addition, the number average molecular weight (Mn) and molecular weight distribution (Mso /M
%) was confirmed by the same method as in Reference Example 10. The structure of the resin thus produced was examined in the same manner as reference f110, and it was found that the molecular terminal of the raw material novolac-type substituted phenol/formaldehyde resin and p-xylylene glycol reacted, and the novolac-type substituted phenol/formaldehyde resin component reacted with p-xylylene glycol. By alternately arranging and connecting units and p-xylylene group component units, the p-molecular weight is increased, and novolac-type substituted phenol/formaldehyde resin component units are bonded to the molecular end of the resulting resin. Make sure my friend. In addition, since this resin is completely soluble in dimethylacetamide, tetrahedron, etc., it is confirmed that it does not contain any three-dimensional crosslinked structure (gelled product) and is substantially linear. Table 6 shows the properties of these resins.
It was shown to.

Reference Examples 22 to 2'5° In Reference Example 10, in place of the low molecular weight novolak p-cresol formaldehyde resin, a low molecular weight novolac type inert-cresol p-cresol having a linear structure having a branched chain as shown in Table 7 was used. Example 9: Using 100 g of cresol formaldehyde cocondensation resin, the procedure was carried out in the same manner as in Reference Example 10, except for Example 9.

The structure of the obtained resin was confirmed by the same method as in Reference Example 10, and the presence of a novolak-type precipitated-cresol-cresol-formaldehyde co-condensed resin skeleton was confirmed. is produced, the raw material low molecular weight novolak l1s-cresol/p-cresol/formaldehyde cocondensation resin reacts with p-xylylene glycol, resulting in a novolac type 1s-cresol/p-cresol/formaldehyde cocondensation resin. The component units and p-xylylene group component units are alternately arranged and connected to increase the molecular weight, and the resulting resin has a novolac cresol/p-cresol/formaldehyde cocondensation resin component at the molecular end. Confirm that the units are connected.

Since these resins completely dissolve in dimethylacetamide, tetrahydrofuran, etc., it was confirmed that they do not contain any three-dimensional crosslinked structure (gelled product) and are substantially linear. These properties are shown in Table 7.〇Example 1 to Example 68. Comparative Examples 1 to 12 High molecular weight novolak-type substituted 31 phenolic resin obtained in Reference Examples 1 to 23 above Cured ordinary low molecular weight novolac-type substituted phenolic resin used as raw material in the above reference examples. The performance of the curable resin composition when blended with mold resin was evaluated. Flame retardancy was evaluated using the UL94 method, and other performance evaluations were performed using conventional methods. When evaluating the performance of a curable assembly, follow one of the following methods to reverse the curable resin composition [see Table 8]
.

Preparation method CA of curable resin composition] Novolac substituted phenol 1111 fat 11, bisphenol 11M epoxy resin for testing shown in Table 8 (
Manufactured by Mitsui Petrochemical Epoxy Co., Ltd., product name: EPOMIK R
-140) 25,9. Fused silica 150j' 1BFs
・2-1f Ayital complex 0.25JI.

Montanic acid wax 0.7i and the flame retardant listed in Table 8 were blended and kneaded on a roll at 80°C.

After cooling, it was crushed into 7 to 100 meshes and sealed at 250"C. After post-kinearing at 250"C for 30 minutes, the physical properties of the molded product were measured and the results shown in Table 8 were obtained.

Preparation method of curable resin composition [B] The test novolac-substituted phenol resin 15JI shown in Table 8, bisphenol A type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., trade name EPOMIK R-14)
0) 25II, fused silica 9511, BFs/2-methylindazole complex 0.25. ? , blended with 0.71% of monchonic acid wax and a flame retardant listed in Table 8, mixed on a roll at 80°C for 7 minutes, cooled, crushed into 7 to 100 meshes, and heated with a gold plate at 250°C. 100 hours/♂ (actual pressure),
Press molding was performed for 20 minutes. This was heated at 250"C for 60 minutes in post-11? air. After that, the physical properties of the molded product were measured and the results shown in Table 8 were obtained. High molecular weight p-cresol formaldehy Y resin 57
L Bisphenol A type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., trade name EPOMICH-140) 659
And a glass cloth (manufactured by Nittobo Co., Ltd., glass cloth WE-18-B
It was impregnated with Z2), depress-molded to 1 at 170°C, and debossed to 8 at 180°C after death to produce a laminate. The bending strength of this laminate was measured at 21°C and 180°C, and the results shown in Table 8 were obtained.

The novolac chick-substituted phenolic resin 15y1 novolak-type phenol-epoxy resin for testing shown in Table 8 (
Manufactured by Nippon Kayaku Co., Ltd., trade name: Epoxidized phenol novolac EPPN-201) 2551, S* Silica 951. BF
0.25M of m-2-methylimidazole complex, 0.75.9% of Montan acid wax, and the flame retardant listed in Table 8 were blended and kneaded for 7 minutes on a roll at 80°C. After cooling, 7
Grind to ~100 mesh pieces, and grind to 100 mesh pieces at 250°C.
Press molded for 20 minutes at KLL/AM (actual pressure). This was subjected to Boston air at 250° C. for 30 minutes, and after death, the physical properties of the molded product were measured and the results shown in Table 8 were obtained.

Preparation of curable resin composition CB'J Novolac-type substituted phenol 11111M, bisphenol A-type epoxy resin for test shown in Table 8 (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., trade name IPOKIK A-14)
0) 25L Nine inorganic fillers shown in Table 8 279. BFa・2
0.25j' of -methylimidazole complex, 0.7i of Montanic acid wax, and those listed in Table 8 were blended together and mixed under heating at 80 DEG C. for 7 minutes. After cooling, grind into 7 to 100 meshes and process at 100 kl/lx in a metal section at 250℃.
(actual pressure), press molded for 20 minutes. This at 250℃
After airing in the post for 50 minutes, the physical properties of the finished product were measured and the results shown in Table 8 were obtained.

True manufacturing method of curable resin composition (J') Table 8 shows Noblak type substituted phenol resin 100#, bisphenol A type epoxy resin (Mitsui Petrochemical Epoxy Co., Ltd. Exhibition, trade name: EPOMIK R-14) as shown in Table 8.
0) 1g1 of 659 and Br3.2-methylimidazole complex and the flame retardant listed in Table 8 were kneaded and mixed, and the mixture was heated at 200°C.
This was press-molded for 20 minutes at 100kl/cm" (actual pressure) in a mold of The physical properties of the molded product are shown in Table 8.
60 g of the novolac-type phenol formaldehyde resin obtained in Comparative Example 2 as cured resin [However, in the comparative example, the novolac-type substituted phenol resin to be tested was not used, and the novolak-type substituted phenol resin obtained in Reference Example 8 was used as the cured resin. The amount of type phenol/formaldehyde resin used was 1009. ], Hexamine 109 as a curing agent
Asbestos 679 was added as a filler, and Bisand 11 stearate and the flame retardant listed in Table 8 were blended to prepare a composition for a molding material. This composition is thoroughly ground and mixed and kneaded for 18 minutes at a temperature of 90 to 110°C, and the kneaded sheet is ground and mixed to form a molding material. Table 8 shows the physical properties of the molded product obtained by molding this at 165° C. and 300 hours/cm for 5 minutes.

mm method CM of curable resin composition] As shown in Table 8, the solid resol obtained in Reference Example 24 as the 70L curable novolac-type substituted phenol resin for testing! 1 phenol formaldehyde resin 30Ii,
Asbestos 67 as a filler, Bisand 11 stearate as an additive and a flame retardant listed in Table 8,
A friend who prepares compositions for molding materials. This composition was sufficiently pulverized and warmed and kneaded with rolls at 120° C. for 15 minutes, and the sheet with the cross-wires completed was pulverized and mixed to obtain a molding material. This is 180
℃, 500! Table 8 shows the physical properties of the molded product obtained by molding under the conditions of 3.5 minutes.

Reference example 24. (Manufacture of solid resol Taki phenol/formaldehyde resin) Phenol 10.09 (11 mol), '57 weight - formalin 90 # CHCH 61.1 mol) and 25 weight - ammonia water 0.5 g were placed in a stoneware, and 90~10
The reaction was carried out at 0° C. for 1.5 hours under reflux. Next! .

The mixture was cooled to room temperature, the separated aqueous layer was removed, and the emulsion of the initial condensate was again heated to 90 to 110°C and dehydrated under reduced pressure. When the temperature of the reactant reached 110° C., the contents were taken out, cooled and solidified to obtain resin 100I. The resin had a number average molecular weight (1%) of 440, a coulometric average molecular weight (CMw) of 740, a molecular weight distribution (Mw/Ms) of 69 as determined by gel pern knee chromatography, and a melting point of 10 as determined by microscopy.
It died at 5℃.

Claims (1)

[Claims] (1) □□□ Hardening! l! Resin, ■ A substantially linear high molecular weight novolac device with a bifunctional phenol component as a living body and a number average molecular weight (M%) of 1500 or more.
1 phenolic resin, and OJIm! A cured MS fat composition containing a refueling agent. (211I high molecular weight novolak substituted phenolic resin (
(G) constitutes the general formula [I)1 (wherein, two of the six R1 are hydrogen atoms, and the remaining one is an alkyl group having 1 to 8 carbon atoms, and 6 R1 is a
1 to 10 aryl groups, halogen atoms, or hydroxyl groups, 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. A phenol component containing at least 70 mol or more of at least one double-blind phenol component represented by J;
Snow-CHo L fl J (wherein, R3 represents one type of substituent selected from the group consisting of a hydrogen atom, a methyl group, and a methyl group. The polymeric novolak-substituted phenol contains a divalent hydrocarbon group in each block of novolac repeating units having a number average molecular weight of 250 to 1200. Chain extending groups consisting of a high molecular weight novolak substituted phenol @'gltQN, N
- The curable resin composition according to claim (1), which has a number average molecular weight of 1500 or more as measured by vapor pressure osmosis in dimethylacetamide Sm. (6) High molecular weight novolac-type substituted phenolic resin (BJ
) The curable resin composition according to claim (1) JJ or claim 0, which is a high molecular weight novolak-type substituted phenol resin having an average molecular weight t; 6; 170,071 and L15,000. (4) High molecular weight novo 2-substituted phenolic resin @
The claimed scope is a high molecular weight novo 2-substituted phenolic resin having a number average molecular weight in the range of 2,000 to 10,000! The curable resin composition according to any one of items (1) to (5). c5) High molecular weight novolac substituted phenolic resin (
b) Number average molecular weight (#s Weight average molecular weight for JK (
Claims (1) to (4) are high molecular weight novolak-type substituted phenolic resins having a molecular weight distribution (J/w/Rs) expressed as a ratio of 47w) in the range of 1.8 to 20. Any of the cured m-resin compositions described in . (6) High molecular weight novolak! Phenol resin replacing j1 @
However, it has substantially the general formula [■] Z+y, -z+%Y-Z(■) (wherein Z is a substantially linear novolak-type repeating unit formed by condensation of the phenol component and the aldehyde component). indicates a block, Y indicates a chain extending group consisting of a divalent hydrocarbon group, p indicates an integer of 〇 or 1, and square indicates an integer of 0 or 1 or more.Has a polymer chain represented by λ The curable resin composition according to any one of claims (1) to 0, which is a novolac-substituted phenolic resin. ■ In the general formula (■), p is 1, and a chain extending group is %FF wherein Y is an alkylidene group having 1 to 4 carbon atoms, a fullkylene group having 2 to 5 carbon atoms, an arylalkylidene group having R prime numbers 7 to 9, or a 7-arylenebisalkylylene group having 8 to 10 carbon atoms; The curable resin composition according to item 6).However, the phenol #4 component constituting the high molecular weight novolak antally substituted phenol resin has a trifunctional content of 30 moles in a casing.
The cured resin composition according to any one of claims (1) to @G'), which is a phenol component containing S-injection phenols. Q) High molecular weight novola'-temperature substituted phenolic resin (b)
The phenolic components that make up the difunctional phenol 9
AJ! A phenol component consisting of 80 to 100 moles of i, and 20 to 20 mole percent of a trifunctional phenol component (however, the ratio of both phenol components is selected to be 100 moles). Claim No. (
The cured resin composition according to any one of items 1) to (B). (υ＾High molecular weight novolak-type substituted phenolic resin c) is composed of 90 to 100 moles of difunctional phenol component (a) and 90 to 10 mole of trifunctional phenol component (however, both phenols The cured resin composition according to any one of claims (1) to (9), wherein the total of the components is 100 mol LsK. ) to high molecular weight novolac-substituted phenolic resin)
The blending ratio is 30 parts by weight per 100 parts by weight of the curable resin.
The curable resin composition according to any one of claims (1) to (10), wherein the amount is in the range of 150 parts by weight. (Claim curable resin (A is a cured mIIM resin that can be cured with a phenolic hydroxyl group-containing compound, and the composition contains the substituted phenolic resin made of molecular weight novolak as a curing agent. Cured MS resin composition according to any one of claims 1 to 11, wherein the curable resin (a) is an epoxy resin. (Claim 1) in which the hook-curing resin (b) is a resol-made phenolic resin or another novolak-type 7-ethanol resin composition. The curable resin composition according to any one of Items 1 to 11. (The S refractor 0 is a refractory resin composition selected from the group consisting of an organic halogen compound, phosphorus or a phosphorus compound, and a combination of these and an antimony compound. The composition according to any one of claims (1) to (14), which is a flame retardant. The composition according to any one of claims (1) to (152), wherein the total weight of the resin (b) is in the range of 2 to 60 parts by weight in terms of 1·oool parts. (1 Special feature in which the force-curing resin composition contains an inorganic filler.
The curable resin composition according to any one of fM range items (1) to (16). (Any one of claims (1) to (17), wherein the blending ratio of the inorganic filler is 60 to 200 parts by weight based on 1 part by weight of the curable resin. A curable resin composition.