JPS60219233A - Diallyl phthalate resin prepreg - Google Patents

Abstract

PURPOSE:The titled prepreg excellent in heat resistance, moisture resistance, impact resistance, dimensional stability, electrical properties, etc., and useful in the production of insulating materials for use in electronics, prepared by impregnating a base with a resin essentially consisting of a diallyl terephthalate copolymer. CONSTITUTION:The titled prepreg prepared by impregnating a base with a diallyl terephthalate copolymer prepared by copolymerizing diallyl terephthalate with an aromatic hydrocarbon having at least one H atom in the benzyl position, represented by the formula (wherein R<1> and R<2> are each H or a lower alkyl, and n=1-3) or a mixture of this copolymer with at least one resin selected from among unsaturated polyester resins, epoxy resins, and epoxyacrylate resins. This prepreg is useful in the production of, chiefly, high-fidelity insulating materials for use in electronics, for example, printed circuit boards, multiwire substrates, multi-layer substrates, and insulating substrates.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diallyl phthalate resin prepreg impregnated with a resin containing a terephthalic acid diallyl ester copolymer as an essential component. Its purpose is mainly to produce highly reliable insulating materials for electronics, such as laminates for manufacturing printed wiring boards, multi-wire boards, hybrid boards, multilayer boards, insulating boards, etc., or circuits,
Heat resistance and dimensional stability for manufacturing films and sheets that protect and bond elements, substrates, heat sinks, etc. 1.
The object of the present invention is to provide a thermocouple with excellent properties such as moisture resistance, impact resistance, and electrical properties.

Recent advances in electronics have been remarkable, and along with this, new materials and application technologies that can support higher speeds and higher densities are being sought. Currently, glass epoxy is widely used as a printed wiring material, but as equipment becomes smaller and multi-functional, its dimensional stability, heat resistance, and moisture resistance are required.

The reality is that they do not necessarily meet various strict requirements regarding reliability and the like.

In other words, as density increases, -C becomes multi-layered, the board thickness increases, and the diameter of the through ball decreases. Also, the stress is concentrated on some corners and the inner layer copper foil, reducing reliability. This problem of dimensional stability is also often a problem when changing in the =J direction in the XYjj direction, and with crow epoxy, the pattern accuracy and positional accuracy necessary for automatic mounting in the component mounting process are insufficient. Furthermore, if the hole pitch is made smaller and the pattern density becomes too large, there is the problem that dielectric breakdown is likely to occur under high temperature and high humidity conditions, so several steps have been taken.

As a result of repeated studies to improve the problems of various materials for insulating substrates as described above, the present inventors found that diallyl terephthalate, which was disclosed in the applicant's earlier application, was used as a resin for use in the above-mentioned materials. 1 stell copolymer patent application No. 57-189981
The present invention was achieved by discovering that the above-mentioned resin is a resin having performance that can meet the above requirements.

In other words, the present invention provides terephthalate obtained by copolymerizing a terephthalic acid diallyl ester and an aromatic hydrocarbon having at least one hydrogen atom at the benzyl position as a base material,
A diallyl phthalate impregnated with a diallyl ester copolymer or a mixture of the copolymer and one or more resins selected from unsaturated polyester resins, epoxy resins, and epoxy acrylate resins. It is a resin prepreg.

The terephthalic acid diallyl ester copolymer used in the present invention (hereinafter simply referred to as diallyl ester copolymer) is the terephthalic acid diallyl ester represented by the formula (1) and the formula (2) (wherein R1 and R2 are respectively Represents a group selected from 8Y consisting of a hydrogen atom and a lower alkyl group, where 1 is 1
terephthalic acid diallyl ester copolymer derived from an aromatic hydrocarbon having at least one hydrogen atom at the benzylic position represented by
a) One monomer unit of formula (2) is attached to the terminal of one unit of formula (1), and the allyl group of the monomer unit of formula (1) and its CI and/or C** carbon-
It has a carbon bonded structure. Furthermore, (b) the number of seven units of the formula (1) in the carbon-carbon bond molecular chain portion formed by the allyl group of the monomer unit of the formula (1) of the copolymer is 3 to
It is a copolymer having a horizontal structural feature of 11 molecules, preferably 3 to 10 g. This terephthalic acid diallyl ester copolymer can be produced by reacting a compound of formula (1) and a compound of formula (2) under specific conditions in the presence of a known organic peroxide or azo compound catalyst. can.

Details of this copolymer are described in Japanese Patent Application No. 57-189981 filed by the present applicant.

The unsaturated polyester used in the present invention includes one or more unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, and mesaconic acid; Basic acids include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid,
Refers to compounds synthesized from one or more types of terephthalic acid and their halides, such as tetrahydrophthalic acid and hexahydrophthalic acid, and polyhydric noflucols such as ethylene glycol and propylene glycol. The selection of each component and the combination U may be determined depending on the use of the prepreg. For example, when a high degree of dimensional stability, heat resistance, etc. is required as a printed wiring board, it is preferable to use a terephthalic acid-based unsaturated polyester because of its good compatibility.

The epoxy resin used in the present invention preferably has an average of at least two epoxy groups per molecule, and examples of such 1-poxy compounds include ethylene glycol.

Ether-type epoxy compounds obtained by the reaction of polyhydric alcohols such as glycerin and trimethylolpropane with epihalohydrin, and glycidyl ethers obtained by the reaction of polyhydric phenols such as resorcinol, hisphenol A, and halogenated bisphenol A with epihalohydrin. Type 1 poxy compounds, novolac type epoxy compounds obtained by the reaction of phenol novolac resins or cresol novolac resins with shrimp halohydrin, epoxy compounds obtained by epoxidizing aliphatic or alicyclic olefins, etc., epoxidized products of polybutadiene, etc. are used. .

These may be selected depending on the use of the prepreg, but for example, when a high degree of dimensional stability and heat resistance is required as a printed wiring board, bisphenol type 1 obtained by the reaction of bisphenol A and epichlorohydrin is used. Preferred are novolak-type epoxy resins obtained by reacting poxy resins or novolak resins with epichlorohydrin.

The epoxy acrylate resin used in the present invention refers to a resin obtained by reacting the epoxy group of the above-mentioned epoxy resin with acrylic acid or methacrylic acid, which is a one-carbon compound.

' The above-mentioned resin to be impregnated into the prepreg of the present invention is a diallyl ester copolymer alone C, or 20-95% by weight of the copolymer and 80-95% by weight of a resin selected from unsaturated polyester resins, epoxy resins, and epoxy acrylate resins. A resin mixture in the range of 5% by weight is used. The purpose of other resins added to the diallyl ester copolymer is to improve the impregnating properties of the impregnating base material and the viewing properties during molding of the '411J prepreg and copper metals, plastic laminates, etc. Therefore, the formulation is highly preferred. However, if the amount of the resin blended is less than 5% by weight, the effect is small, and if it exceeds 80% by weight, the excellent dimensional stability and electrical properties of the diallyl ester copolymer,
Heat resistance, chemical resistance, toughness. Performance such as impact resistance cannot be fully demonstrated.

The resin for impregnation of the present invention may optionally contain a vinyl thread binder, an allyl monomer, or an oligomer thereof that can be copolymerized with the resin. Examples of these include diallyl orthophthalate, diallyl isoftasy 1
-, diallyl terephthalate, diallyltetrachloro or bromoortho, iso, and terephthalate, diallylchlorendate.

triallyl isocyanurate, triallyl cyanurate-1
-, triallyl trimellitate, 1-lylyl bosphate, styrene, α-chlorostyrene, methyl (meth)
Acrylate.

Butyl (meth)acrylate, ethylene glycol di(
meth)acrylate, propylene glycol di(meth)
Acrylate, trimethylolpropane tri(meth)acrylate.

Methyl acrylate acrylamide, diacetone acrylamide, N-vinylcarbazone bisacrylamide, methacrylamide.

N-tert-butylacrylamide, 2.4- or 2.6-t-lylene diisocyanate, maleic acid semiester, phthalic acid monoallyl ester, etc., or low molecular weight polymers thereof, diazuruortho. Examples include iso and terephthalate prepolymers, and these can be used alone or in an appropriate combination of two or more. In particular, the addition of diallyl isophthalate and diallyl terephthalate is preferable because it improves the impregnating property of the resin component into the base material for impregnation and the pressing properties when applied to prepreg. The appropriate amount of these hexamers to be blended is 40 parts by weight or less based on 100 parts by weight of the total resin content. If the amount exceeds 40 parts by weight, the curing speed will be unduly delayed, the distortion of the laminate will increase due to increased curing shrinkage, warping, and dimensional stability will decrease, and the properties of the resin component of the present invention will deteriorate. cause it to happen.

Among the resins for impregnation of the present invention, the curing agents for resin components other than epoxy resins include dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, diaryl peroxides, and ketones such as methyl ethyl ketone peroxide and cyclohexanone peroxide. Peroxide; 1,1-bis(tert-butylperoxy), -3,3,5-
Peroxyketals such as trimethylcyclohexane: Hydroperoxides such as cumene hydroperoxide: lauroyl peroxide, benzoyl peroxide, 2 peroxide,
sialoyl peroxide and diacyl peroxide such as 4-dichlorobenzoyl; peroxycarbonates such as diisopropyl peroxydicarbonate: tert-butyl peroxyacetate, tert-butyl peroxyvivalate, tert-butyl peroxyoctoate,
Examples include peroxy esters such as tert-butylperoxyhenzoate, and azo compounds such as azohisisobutyronitrile other than the above-mentioned organic peroxides can also be used. These curing agents can be used alone or in combination of two or more. The appropriate amount is 0.1 to 6 parts by weight per 100 parts by weight of the resin.

In addition, as a curing accelerator, for example, metal soaps such as cobalt salts, vanadium salts, and mankan salts of naphthenic acid or octoic acid, and aromatic tertiary amines such as dimethylaniline and diethylaniline are added to 100 parts by weight of the resin. Range C may be added in an amount of 0.005 to 6 parts by weight.

When C1 boxy resin is used as the impregnating resin of the present invention, aliphatic polyamides such as dicyandiamide, aromatic amines, and m-acid anhydrides are used as curing agents. A curing agent with which the reaction does not proceed is preferably used.

Examples of aromatic amines include metaphenylenediamine, xylylenediamine, diaminodiphenylmethane,
Examples include Diaminoschif J Nilsulfone and benzyldimethylamine.

Examples of organic acid anhydrides include hydrothermal phthalic acid, tetrahydrophthalic anhydride, maleic anhydride, chlorendic anhydride, pyromellitic anhydride, 3.3=, 4.4
”-benzophenone tetracarboxylic anhydride, methyl succinic anhydride, dodecyl succinic anhydride, anhydride 11
Examples include lucuccinic acid and quinahydronotaric anhydride.

A mixture of an aromatic amine and an organic acid anhydride or a eutectic white modified product may also be used, and if necessary, a small amount of aliphatic amine may be added. The amount of these curing agents used is 0.5 to 1.5 per gram of epoxy resin.
Corresponds to gram equivalent. All you have to do is make it so.

Various compounding agents may be added to the impregnating resin of the present invention depending on the intended use of the prepreg. For example, white carbon, titanium oxide, diatomaceous earth. Fillers or pigments such as mica and montmorillonite are blended to make the prepreg surface hydrophilic, antimony trioxide provides flame retardancy, and polymerization is used to improve storage stability and adjust curing speed. Inhibitors may also be added.

Examples of the base material used in the prepreg of the present invention include natural edges III, woven fibers made of synthetic fibers and synthetic resins, non-woven materials B, paper, and mats.

For example, materials include cellulose, natural fibers such as cotton and asbestos, inorganic fibers such as ceramics, fibers, and glass fibers, polyamide, and polyimide.

Examples include synthetic fibers such as polyimide amide and polyester. In particular, when using an inorganic base material, vinyltriethoxysilane, vinyltris(2-methyl-oxyethoxysilane)
・Kysi) Silane.

Vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, aminosilanes such as γ-amino-10-pyltriethoxysilane, N-β-(aminoconityl)-γ-aminopropyltrimethoxysilane, γ-glycyl-1-xy10-pyltrimethoxysilane, It is preferable to use silane coupling agents such as epoxysilanes such as 1 to xysilane to improve adhesion to the resin.

In producing the prepreg of the present invention, first, the above-mentioned impregnating resin, resin curing agent, and other monomers and compounding agents are
Preferably, the resin is dissolved in a solvent to prepare a resin solution for impregnation or coating.

Examples of solvents include acetone, aliphatic carbons such as methyl ethyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzenes, methylene chloride, chloroform, etc. Examples include halogenated hydrocarbons, acetate esters of diethylene glycol monoalkyl ether, etc., and one or more of these can be selected and used.

The amount of solvent to be used may be adjusted depending on the solubility of each component, the method of supporting it on the substrate, i.e. impregnation method or coating method, and the amount of resin to be supported, but usually the resin content of the present invention is 100%. It is not more than 300 parts by weight.

The method for supporting the resin on the base material may be an impregnation method or a coating method using an applicator, comma coater, bar coater, gravure coater, 70 coater, spray coater, etc., depending on the type of base material and the viscosity of the resin liquid. can.

The amount of resin supported on the base material is not particularly limited, but it is usually selected in the range of 50 to 1,500 parts by weight per 100 parts of the base material depending on the type of base material and the intended use of the prepreg. good.

Prepregs coated with or impregnated with resin undergo a drying process to remove volatile components. When drying in batches, for example, drying at room temperature for about 0.2 to about 1 hour, followed by drying at 40 to 120°C for about 3 to about 30 minutes (+2. When using a curing agent with a low temperature, it is necessary to avoid combinations of drying conditions that involve high temperatures and long periods of time.

Of course, it is possible to perform the coating step or impregnation step and the drying step continuously, and commercially available impregnation machines, coating machines, dryers, etc. can be used.

By curing the prepreg thus obtained, it can be used in a wide range of applications as a laminate, an adhesive or a protective film or sheet. In particular, its characteristics are best demonstrated when used as electrical and electronic components and materials. For example, when using printed circuit board 1 in the form of a laminated board by binding an FA board to print board 1, when the wiring board is fabricated using various methods such as the substructural method, additive method, semi-additive method, etc., through-holes may be required for double-sided or multi-layered wiring boards. It is desirable that the ball be plated, so that the conductivity of the through hole can be maintained well even under changes in environmental conditions such as repeated heating and cooling, and that reliability is high. In a thermal cycle test in which one cycle was 30 minutes at -65°C and 30 minutes at +125°C, the printed lfAM board using the prepreg of the present invention showed a value change of 5 after 1000 cycles.
．． It is extremely superior to within 0%, and is a significant improvement compared to conventional substrates made of phenolic resin or the like.

In addition, there is extremely little change in insulation resistance under high temperature and high humidity conditions, significantly improving reliability.

More importantly, as automation such as component mounting robots progresses, improved positioning accuracy is required.
In the printed wiring board using the prepreg of the present invention, ■ Tsuching, resist printing, etc. are carried out to the greatest extent possible (=J, etc.) by minimizing dimensional changes before and after each heat treatment process.
It has characteristics that can fully meet the demands of the industry, such as strength.

In addition, after manufacturing a laminate using the prepreg of the present invention and forming a circuit, or at the same time as forming a circuit, laminating it with another laminate via the prepreg of the present invention,
For example, if hot pressure molding is performed, each laminate will adhere to each other and be integrated. Of course, the prepreg can be used as a contact layer, and if this method is extended, a multilayer board can be easily manufactured. Conventional diallyl phthalate resin has superior electrical properties.

Although it has dimensional stability, it lacks adhesion, once cured, it does not adhere to other resins of the same type, and modification with other resins to compensate for these drawbacks is limited due to poor compatibility. However, the prepreg of the present invention not only further improves the excellent properties of conventional diallyl phthalate resins but also enables adhesion after curing. r:ii
! This is due to the excellent properties of the diallyl ester copolymer, which is an essential component of the prepreg resin composition.

The present invention will be specifically explained below with reference to Examples, and the use of the prepreg of the present invention will be explained below. Since there are many types of E, we will only show some of them, and are not limited to these.

Production examples 1 and 2 of prephthalic acid diallyl ester copolymer Equipped with a turbine blade type variable stirrer, a double pipe type supply nozzle for monomer and catalyst supply, a nitrogen persilo, a leak valve, a sampling port, a thermometer and a pressure gauge. inner diameter 600vn,
A jacketed polymerization tank made of 5US304 and having an internal volume of 12o1 was used. The double-pipe supply nozzle for monomer and catalyst supply is installed below the liquid level in the body of the polymerization tank. Three such nozzles were installed in order to minimize the residence time so that λ+i < L/k o in case of nozzle blockage. A sampling port was also installed in the body of the polymerization tank, making it possible to collect samples of the liquid phase using the inner tank during the polymerization reaction. An oil rotary military pump and a nitrogen cylinder are connected to the nitrogen persilo, which can be switched as needed.

1. Into the polymerization layer, 60 kg of aromatic hydrocarbon (HC) of formula (2) shown in Table 1 below was charged, and the pressure was reduced using a vacuum pump at the claw part, and the nitrogen gas was used to return the pressure to the polymerization layer. After exchanging the air in the tank with nitrogen three times, the pressure was reduced again and the mixed layer was tightly sealed with IM1.Start the stirrer and turn on the v240PP.
While stirring with M, steam was passed through the jacket and the temperature was raised to a humidity of 140°C.

The stirring speed was increased to 720 PPM, and terephthalic acid diallyl ester was pumped through the outer pipe of the double pipe nozzle at the specified speed, and di-tert-butyl peroxide (
f) T B I) O and formula (2) aromatic hydrocarbon (
HC) were mixed in advance at a molar ratio of 0.5:1 and supplied to the polymerization tank at a predetermined speed using a pump with a discharge pressure of 70 kg/cat. The steam was adjusted to maintain a temperature of 740°C. In addition, the formula (1) terephthalic acid diallyl ester (
DAT") was cooled to 15°C, the mixture of di-tert-butyl peroxide and aromatic hydrocarbon was cooled to 5'C, and the piping leading to the polymerization tank was kept cool. The pressure of the polymerization tank was 0.3~ It was 9/cnG in 2.

When the specified supply of terephthalic acid diallyl ester, aromatic hydrocarbon, and di-tert-butyl peroxide is completed, the steam is stopped and the stirring speed is lowered to 24 ORP.
M, and cooled by passing cooling water through the jacket. After cooling to around room temperature, open the leak valve and return to normal pressure.
The polymerization reaction was completed.

During the polymerization reaction, samples were appropriately taken from the sampling port and the refractive index of C11m and G11. The reaction was followed at C.

The feed rates and amounts of diallyl terephthalate, aromatic hydrocarbons, and di-tert-butyl peroxide are shown in Table 1 below.The polymerization reaction solution obtained above was evaporated using a thin film evaporator. of unreacted aromatic hydrocarbons in the evaporation residue.
Combination of copolymer and unreacted diallyl prephthalate 1 ster
(The ratio by weight to
The mixture was added dropwise to a stirring tank containing 518 methanol by weight and stirred to precipitate a co-Φ compound. The precipitated copolymer was thoroughly washed with the same amount of methanol, filtered, dried, and pulverized to obtain a powdery copolymer.

Table 1 shows the yield and physical properties of the copolymer.

Table 1 In Table 1 above, C (1) is the measured value of polystyrene conversion by glupermeation chromatography C1 manufactured by Waters Inc.
IC using a 150CG P CJ device.

For (2), a light transmission type automatic melting point measuring device manufactured by Metgy Co., Ltd. 1' F 61J was used.

Examples 1-15. Comparative Examples 1 to 5 Using the diallyl ester copolymer of Production Example 1.2, CC
Resin liquids for impregnation were prepared as shown in Table 20.

The edge materials shown in Table 3 were impregnated with these impregnating resin liquids and air-dried at room temperature for at least 5 minutes at 90-130°C r1.
Prepregs with each resin content were prepared by drying with hot air for 0 minutes.

The obtained prepregs were stacked with copper foil (TC manufactured by Nikko Gould Co., Ltd.) with a thickness of 35 μm on both sides of the prepregs as shown in Table 3, and then formed using a predetermined -C strip A9 to obtain a copper-clad laminate. General physical property test (JISC) for each laminate as a copper clad laminate
-6481) and the results are shown in Table 3.

In Table 3, the resin gold ω of the prepreg is expressed as i01 after drying per 100 g of the base material. The base materials used are as follows.

A Nigarasu cloth r K S 1600- S 910
B Nigarasu cloth r K S 1600-3920JC made by J Riki Nebo Glass Fiber Co., Ltd.
:Glass cloth r K S 1600-S 940L
JD: Kevlar cloth rK 120-ES 1" E Nigaras mat r EP 4050J Manufactured by Japan Vilene Co., Ltd. F: Kevlar cloth [120-EX IJ Manufactured by Kanebo Glass Company G Nigarasu cloth r K S 1200-S 910
The J physical property test was conducted under the following processing conditions.

Volume resistivity upper row: C-(16/ 20/ 65 lower row: C-96/ 20/ (i5+ C-96/
40/90 Surface resistance Upper row: C~96/20/65 Lower row: C-96/20/65 〇 -96/4
0/90 insulation resistance Upper row: C-96/20/65 Lower row: C-96/20/65+ D-2/1
00 dielectric constant Upper row: C-96/ 20/ 65 Lower row: C-96/ 20/ 65 + D-48/ 5
0 Dissipation factor Upper row: C-96/ 20/ 65 Lower row: C-96/ 20/ 65+ D-48/
50 Copper peeling strength After soldering = 260°C - 20 seconds heating: E -1/ 105 Chemical resistance Tri-Clean: After boiling for 5 minutes, water absorption after immersing in a 10% solution of Carini cyanide at 70°C for 30 minutes : E-24150+ D-24/30 As a comparative example, a prepreg prepared in the same manner as in the example using an impregnating resin liquid containing diallyl phthalate resin as a main component was also subjected to the same procedure.

As is clear from the results in Table 3, the resin using the diallyl ester copolymer of the present invention as an essential component was more effective at moisture absorption (C -96/40/90.
D-2/100 or D-48150), it is recognized that the change is small and the water absorption rate is also small. Furthermore, in terms of heat resistance, those using the resin of the present invention are clearly superior.

Example 16. Comparative Example 6 Using copper-clad laminates of Example 1.4.5.8 and Comparative Example 1.3, 4°5, a through hole 1 with a diameter of 0.9n was made
A circuit with a circuit width of 11 m including 50 holes was provided, and the conduction resistance was determined to be 1j at both ends of the circuit. Then, it was subjected to 100 cycles of heating and cooling at -65°C (30 minutes) and 125°C (30 minutes).
The experiment was repeated 0 times, and the changes in conduction resistance were measured and shown in Table 4. The numerical value for each time is shown as the average value of 3 samples.

As a comparative example, a commercially available copper clad laminate (FR-4) was similarly measured.

Table 4 Example 17. Comparative Example 7 Example 1.4. Using the copper-clad laminate obtained in '5.8 and the commercial product used in Comparative Example 6, it was subjected to (1) a copper foil etching process using iron chloride (80°C, 30 minutes), (2) thermosetting. A step of performing Tsuruta resist treatment (140°C, 30 minutes), (3) a step of performing soldering by flow soldering (
240° C. for 30 minutes), and the dimensional changes of the laminate during this period were measured, and the results are shown in Table 5. The measurement shows the average value C of 5 samples.

Table 5 Procedural amendment (spontaneous) October 24, 1980 1, Case description 1981 Patent Application No. 77072 2,
Name of the invention Diaryl phthalate resin prepreg 3,
Relationship with the case of the person making the amendment Patent applicant 4, agent 1-10-8-6, Edobori, Nishi-ku, Osaka 550 Contents of the amendment (1) Changed "heat resistance" to "heat resistance" on page 8, line 11 for the specification. ``Sex'', corrected.

(2) Ibid. No. 27, line 1 directly below [105J is corrected to [125J].

(3) Same @ page 29, second line of note (9) at the bottom of Table 2: “Oxidation”
is corrected to "acid value".

(4) Line 3, directly below No. 32 of the same book, “average value J” is “average value (Ω
〉” and corrected.

(5> Page 33, Table 4, lower box 2 rows in the left column “Change (times)
Correct J to "amount of change (Ω)".

(6) Line 4, directly below No. 33 of the same book [Correct 30 minutes j to ``30 seconds.''

(7) In the third line directly below No. 33 of the same book, ``Dimension change'' is corrected to ``Dimension change (shrinkage rate)''.

Claims (1)

[Scope of Claims] The following terephthalic acid diallyl ester copolymer or said copolymer and one or more selected from unsaturated polyester resin, epoxy resin, and epoxy acrylate (~resin) A diallylphtasy 1-based resin Bripreg is obtained by impregnating a mixture with a resin of Refers to a copolymer with an aromatic hydrocarbon having 1 hydrogen atom.However, in the above formula, R1 and R2 each represent a hydrogen atom and a lower alkyl group selected from the group consisting of:
TL = an integer from 1 to 3.