JPS60139749A - Phenolic resin composition - Google Patents

Abstract

PURPOSE:A phenolic resin composition having excellent heat resistance, moisture resistance, and fast-hardening properties, containing a phenolic resin with a biphenol structure in its skeleton. CONSTITUTION:A resin composition containing a phenolic resin having, in its skeleton, a biphenol structure such as a polymer of biphenols and aldehydes, a copolymer of biphenols, phenols, and aldehydes, and a copolymer of biphenols, alkylbenzenes, and aldehydes. The introduction of a biphenol structure into its skeleton will markedly increase the strength of resin itself and after crosslinked. This is probably because biphenol has not only a rigid structure of benzene rings directly bonded with each other, but also a low OH equivalent, effecting a high strength crosslinking.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a phenolic resin composition that has excellent curability, heat resistance, and moisture resistance. It's there.

It is a well-known fact that in recent years, metal parts and ceramic parts have been replaced with plastic at an unprecedented rate. Phenol resin, polyester resin, epoxy resin, etc. are used as plastics, and they are widely used in the automobile field. Recent trends in these fields include the miniaturization of VTRs, the lighter weight of automobiles, and the increasing probability that Japanese products will be used all over the world. Therefore, there is a strong demand for parts used in these applications to be smaller, lighter, more resistant to environmental changes, and lower in cost.

For this reason, it has become necessary to improve the heat resistance and moisture resistance of the plastic material itself, and to reduce the cost.

The present invention consists of 1. The object of the present invention is to provide a phenol The present invention provides the following CI)・Φ]・
(1) ¥'t' 1: The phenol resin composition includes all the features and features of including in the composition a phenol resin having a biphenol structure in its skeleton.

(1) Polymers of biphenols and aldehydes - Copolymers of biphenols, 7 enols, and aldehydes.

(b) Biphenols and alkylbenzenes Refers to all copolymers of Jl, alde, and humans and biphenol derivatives, such as diphenols and alkylbiphenols.

In addition, phenols refer to phenol, alkylphenol, and resorcinol, and alkylbenzenes refer to toluene, xylene, acenaphthene, anthracene, etc. Aldehydes refer to those having an aldehyde fund, such as formaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, privylaldehyde, and acrolein. Furthermore, the phenol resin composition has a biphenol structure in its skeleton (hereinafter referred to as biphenol type phenol + f).
It refers to anything that contains phenol + V (fat, curing agent, curing accelerator, filler, pigment, molding agent, ice surface treatment agent, etc.) (referred to as l Bft) in its composition. will be accomplished. It is also used as a curing agent for epoxy resins.
These are also included in the phenolic fat composition referred to in the present invention.

The phenol resin mentioned here essentially includes the uninvented biphenol type phenol 1 fat, and it does not apply even if it is used in combination with other phenol 481m 7 A'sB or fake u or more. However, the biphenol diphenol of the present invention
□-The higher the ratio of resin, the faster curing and heat resistance d:
Same as above. In addition, fillers include wood flour, calcium carbonate, and
/-・Asbestos, glass, silica, and scum layer class scum or general A have a history. The curing agent is Novolak RLJ II, a 4-go curing agent! 71 [For example, hequinamethylenetetramine, 1ip of acetic acid; the agent is a curing catalyst such as calcium hydroxide, water, 1-zolized magfu'J-, etc. Surface, treatment, #J refers to a filler modifier for silane coupling AU, and a combustion agent refers to phosphorus, a single compound, a phosphorus compound, etc.

Uninvented biphenol type phenol resin all epoxy toilet fat lll+! The conjugation used as a curing agent can be used alone or with other curing agents such as phenol novolaks, amines,
I! & It may be used in combination with water-based chicken, etc. However, if the ratio 4 of the biphenol type phenol side fat of the present invention is increased,
gi hardenability and heat resistance are improved.

As an epoxy resin composition for Machinizumi parts (RI epoxy resin is a cresol novolac type epoxy resin, the curing agent is a biphenol type phenol resin according to the present invention, using more than half of the gold, the rest is phenol novolac, and the filler is silica). desirable.

The present invention is based on the discovery that the strength of the resin itself and the rj 11 degrees after crosslinking can be significantly improved by incorporating biphenol into the skeleton. This is because biphenol not only has a rigid structure in which benzene rings are directly bonded, but also has a small OH equivalent and can achieve strong crosslinking.

As a result, not only did the curing reaction become faster and quick curing properties were obtained, but also advantages were obtained in terms of heat resistance and moisture resistance as the thermal decomposition temperature of the cured product became higher and the water absorption rate decreased. Is fast curing a high-cycle rationalization of molding and pressing processes? = r Me, which leads to cost reduction, and the heat resistance and moisture resistance mentioned above will support the purchase of glass snack parts when they are made thinner and smaller. The '7m 1Jt of biphenol type phenolic resin mta depends on the ratio of biphenol.

The higher the ratio of biphenol is, the higher the strength is, so it is necessary to determine the use of the enol in the resin and the biphenol-type phenol cutting fat in the composition depending on the purpose. From the viewpoint of strength, it is preferable that 50% or more of the stool fat is biphenol.

The following will be explained based on examples. It should be noted that all figures used in the Examples are parts by weight. Also, the details of the phenolic resin used in the examples can be traced.

■ Tetramenalbiphenol formaldehyde novolac (resin of the present invention), tetramethylbiphenol 698F and 37% formalin 195% in the presence of trifluorochloride 1.52% after reflux reaction for 2 hours, normal pressure/IO heat Solid resin obtained by dehydration (molecular weight 600) Biphenol formaldehyde novolac (Tree of Invention): Biphenol 5581 and 37q6 formalin 195v
Isomorphic resin (molecular weight 600
) ■ Phenol novolac: Mitsui Toatsu (IE #2
000■ Phenol novolac: Nipponka 4(c)PN
”-100 implementation Vj1 Phenol + 1 fat lOO parts, hexamethylenetetramine (manufactured by Sumitomo Chemical (closed)) 20 parts, wood flour 60 parts, charcoal T yield calcium 30 +y+t, calcium hydroxide 2 parts,
7 at 100℃ after mixing 2 parts of carbon and 2 parts of stearic acid.
Knead for 3 minutes using a JIl hot roll to make a separate molding material. At this time, as phenol + 11 April 11 (, J), ■, (i)
, /■-2/1■/■-1/2 I obtained 4 level gold-filled 4 divine materials. The curability, shrinkage rate of these molding materials,
Insulation resistance, thermal deformation (it + l IJf: S water absorption rate is 7.1.4). From axis (1) in Table 1, as a lid type material according to the present invention, i.e., phenol constant resin.
■/(3)=2/1 (1)/■=1/2 It can be seen that the product using (1)/■=1/2 is superior in all properties to the current J11 regular molding material (phenolic resin with kumquats added). . Father, these are the ones with a higher ratio of (1) in the phenolic resin! It can also be seen that more Samurai will appear.

Example 2 Epoxy 4Qr IJf [5-Bagaigy (middle) 1'
=CN 1273] 20 parts, Phenol Jugetsu 10 pieces +
1. Bath-fused silica [manufactured by Toshiba Ceramics (closed)] 'lO section, hardening accelerator [Shikoku Kasei (closed) 2 P Z ) 0.2t
ilt, milan coupling agent [tone silicone (
Co., Ltd. SH-6040] 0.5, mold release agent [Hoechst Japan (closed) Hoechst Wax C] 0.5 after mixing 1
A molding material was prepared by mixing in a 20'O heating kneader.

As this J protector phenol 4 so January effect ■, ■, (21/
■ = 1/2, (V ■ = 2/l, 4 levels are taken!
material was obtained.

Molding materials: hardenability, molding yield, thermal expansion properties,
Water absorption rate, 41 resistance, 53 properties were all investigated. The result is the second garment, B
In i1'), the molding material according to the present invention, that is, phenolic resin, and L2 (■, ■/■ = 1/2, ■/■ = 2/1) were used as the current general-purpose molding material (phenol 4v IM). It can be seen that the curability, heat resistance, and moisture resistance are better than those using It can also be seen that the higher the ratio of biphenol-type phenol sesame, the more these bancho will appear.

Table 1 (Results of investigation using phenol resin molding material) Table 2 (Results of investigation using epoxy resin molding material) Temperature cycle test; 16-pin DIP type IC with 4 x 6 mock consonants all-65 samples ℃ 0 room temperature o 200-c no fever piece 4! Evaluation based on the number of cycles until resin cracks occur in the Ak sample

Claims (1)

[Claims] Polymers of biphenols and aldehydes, co-t4 (compounds of biphenols, phenols and aldehydes,
1. A phenol resin composition characterized in that the composition contains a phenol resin having a biphenol structure expressed as a copolymer of biphenols, alkylbenzenes, and aldehydes in its skeleton.