JPH03210314A - Laminating resin composition and laminate prepared by using same - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a laminate having good mechanical properties, good punchability around room temperature and high rigidity at high temperatures by mixing an allyl-terminated polyester resin with a radical-polymerizable liquid crosslinking monomer. CONSTITUTION:The title composition is one comprising 40-90wt.%, desirably 50-90wt.% allyl ester resin (a resin prepared by incorporating allyl ester groups in the terminals of a polyester comprising a polybasic acid and a polyhydric alcohol) and 5-60wt.%, desirably 10-50wt.% radical-polymerizable liquid crosslinking monomer (e.g. diallyl terephthalate) and giving a cured product with a glass transition temperature of 20-90 deg.C.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a resin composition for a laminate used in manufacturing a laminate used in electrical equipment, electronic equipment, communication equipment, etc., and a resin composition using the same. The invention relates to manufactured laminates.

``Prior art'' Conventionally, resin compositions for laminates have generally been based on phenolic resins, epoxy resins, etc., and these resin compositions have been used as base materials for paper, glass cloth, etc. A laminate is manufactured by impregnating the impregnated material and heating and pressurizing the impregnated product. Here, the term laminate refers to a laminate having a thickness of 0.5 to 5-5, which is used, for example, in printed wiring boards for mounting various electronic components.

When manufacturing a laminate using the above-mentioned phenolic resin or epoxy resin, the resin is usually dissolved in a solvent to form a solution, the base material is impregnated with this solution, and the solvent is removed from the impregnated base material to form a prepreg. A laminate was produced by forming an intermediate called prepreg and laminating the prepregs under high temperature and pressure. However, when laminates are manufactured using this prepreg method, large-scale equipment is required to recover or process unnecessary solvents, and high-pressure presses are required to press the prepreg at high temperatures. There are manufacturing issues such as:

Furthermore, in recent years, laminates made of unsaturated polyester resins have been proposed. Laminated boards using this unsaturated polyester resin are cured through a radical polymerization reaction, so the reaction time is short, and solvent recovery is not required, which eliminates the manufacturing problems that occur when using phenolic resins and epoxy resins. It is something to be solved.

``Problem to be Solved by the Invention'' By the way, when a laminate is actually used for printed circuit boards, etc., it is often punched to form a mold or drill holes. It is required that cracks, whitening, etc. do not occur (hereinafter referred to as punching characteristics). Particularly in recent years, high dimensional accuracy has been required for the position and size of holes in printed circuit boards, etc., and to meet these demands, punching must be performed at temperatures close to room temperature, with few errors due to thermal shrinkage. There is. Therefore,
A laminate that can be punched at a temperature closer to room temperature, that is, has good punching characteristics at temperatures near room temperature, is desired.

Generally, in order to obtain good punching characteristics, it is necessary to bring the glass transition temperature (hereinafter referred to as Tg) of the cured resin used in the laminate close to the temperature during punching. This is because if 'rg of the cured resin material is too high than the punching temperature, cracks will occur in the punched part of the laminate during punching, and if 'rg is too low, the punched part will turn white.

However, the laminate using the above-mentioned unsaturated polyester resin is designed to improve the punching characteristics of the laminate at temperatures near room temperature by lowering the Tg of the cured resin used. However, such a laminate has a drawback in that its mechanical strength, particularly its rigidity at high temperatures, is low.

The present invention was made in view of the above circumstances, and it is possible to obtain a laminate with excellent productivity, good mechanical properties, good punching properties near room temperature, and high rigidity at high temperatures. The object of the present invention is to provide a resin composition for a laminate that can be used and a laminate manufactured using the same.

"Means for Solving the Problems" As a result of various studies, the present inventors found that an allyl ester tree having an allyl ester group at the end of a polyester composed of a polybasic acid and a polyhydric alcohol 1 (A) 40- 95
weight% and radically polymerizable liquid crosslinking monomer (B
) 5 to 60% by weight and has a Tg of 20 to 90°C, and a laminate produced using this resin composition has found that the above object can be achieved, and the present invention This led to the completion of the invention.

That is, the present invention aims to solve the problems in manufacturing paper-based phenolic resin laminates, glass cloth-based epoxy resin laminates, etc., and to invent the above-mentioned resin composition that can manufacture laminates without using the blip-1-nog method. Moreover, by setting the Tg of the cured product of this resin composition to 20 to 90°C, it is possible to obtain a laminate that has good punching characteristics at temperatures near room temperature and high physical properties when hot. I wish I could do it.

Hereinafter, the resin composition for a laminate of the present invention and a laminate manufactured using this resin composition will be explained in detail.

The allyl ester resin (A) used in the resin composition for laminates of the present invention is a polyester composed of a polybasic acid and a polyhydric alcohol, and has an allyl ester group at at least one terminal end.

Examples of the polybasic acids include dibasic acids such as orthophthalic acid, orthophthalic anhydride, isophthalic acid, phthalic acids such as terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and methylendomethylenetetrahydrophthalic acid. Hydrophthalic acids such as phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid and their acid anhydrides, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid, tetrabromophthalic acid, and tetrabromphthalic acid. chlorophthalic acid,
Examples include chlorogenated dibasic acids such as chlorendic acid and acid anhydrides thereof, and examples of trifunctional or higher functional polybasic acids include trimellitic acid, pyromellitic acid, and acid anhydrides thereof. These polybasic acids can be used alone or in combination.

In addition, polyhydric alcohols include ethylene glycol,
Contains aliphatic, alicyclic or aromatic compounds such as 1.2-propylene glycol, 1.4-butanediol, 1.6-hexanediol, neopentyl glycol, l,4-cyclohexane dimetatool, paraxylene glycol, etc. In addition to dihydric alcohols, fIo (ClIC1l*
O) n tl (R is hydrogen or a chain alkyl group, n is an integer of 2 to 10) dihydric alcohols obtained by addition reaction of alkylene oxides such as ethylene oxide and propylene oxide. It will be done.

Examples of trihydric or higher polyhydric alcohols include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol and sorbitol.

In addition, aliphatic compounds containing halogen atoms, such as dibrome neopentyl glycol and tetrabrome bisphenol A adducts of ethylene oxide and propylene oxide,
Examples include alicyclic and aromatic halogenated polyhydric alcohols. These can be used alone or in combination.

The method for producing the allyl ester resin (A) may be any known method, such as the method proposed in Japanese Patent Application No. 63-262217, and is not particularly limited.

For example, there is a method in which a diallyl ester of a dibasic acid such as diallyl terephthalate and the above-mentioned polyhydric alcohol are charged into a reactor together with a transesterification catalyst and reacted while distilling off allyl alcohol-21/. In addition, as an industrially more effective method, instead of diallyl terephthalate, a dialkyl ester of a dibasic acid such as dimethyl terephthalate and allyl alcohol are charged into a reactor together with a polyhydric alcohol and an ester conversion catalyst, and alcohols such as methanol are produced. A method is used in which the reaction is carried out while distilling off. Further, depending on the reaction temperature, a polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution.

In this way, an allyl ester resin (A) having an allyl group at at least one end of the polyester is produced.

This allyl ester tree 11i5(A) may be used as Ill or as a mixture of two or more types.

Moreover, the crosslinkable monomer (n) used in the present invention is
This refers to a monomer having a carbon-carbon double bond that can be radically polymerized, and includes monomers that can dissolve the allyl ester resin (A) and those that can disperse fine solids.

Such crosslinking monomers (B) include, for example, diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, styrene, α-methylstyrene,
Chlorstyrene, vinyltoluene, divinylbenzene,
Methyl (meth)acrylate, edyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid-2
- Ethylhexyl, lauryl (meth)acrylate, benzyl (meth)acrylate, acrylonitrile, vinyl acetate, allyl acetate, acrylamide, vinyl chloride, and the like.

These crosslinkable monomers (B) may be used alone or in combination of two or more.

In the resin composition for a laminate of the present invention, a radical curing catalyst such as an organic peroxide that is commonly used for curing unsaturated polyester resins, diallyl phthalate resins, etc. is used.

Further, flame retardants, colorants, mold release agents, or various inorganic fillers may be added as necessary.

In the present invention, flj of allyl ester resin (A)
h (40 to 95% by weight, preferably 50 to 90% by weight, and the amount of crosslinking monomer (B) is 5 to 60% by weight)
, preferably within the range of 10 to 50% by weight.

If the allyl ester resin (A) is less than 40% by weight, the crosslinking density will decrease and the original heat resistance will decrease.
If the amount is more than 9511% by weight, the viscosity becomes high and it becomes difficult to handle when impregnating a base material, which is not preferable.

Moreover, in the present invention, it is preferable that the Tg of the cured product of the laminate resin composition is within the range of 20 to 90°C.

This is because if the Tg of the cured product is lower than 20°C, when a laminate using such a laminate resin composition is punched at a temperature near room temperature, a whitening phenomenon occurs in the punched part, which is undesirable. This is because if the Tg of the cured product is higher than 90° C., when a laminate using such a laminate resin composition is punched at a temperature near room temperature, cracks tend to form in the punched portion, which is undesirable.

Here, in the present invention, 'rg' refers to a value measured by a thermal stress strain measuring device.

The Tg of the cured product of the resin composition for laminates in the present invention is adjusted by selecting the type of polybasic acid and polyhydric alcohol mentioned above, the molecular weight of polyester, the type of radically polymerizable crosslinking monomer, and the amount added. It is something that will be done.

- Examples of compositions of cured products with rg of 20 to 90°C are shown in Table 1. Note that the resin composition for a laminate of the present invention is not limited to these examples.

(Hereinafter, blank space.) No. 1 to No. 7 in Table 1 are the ones in which the type of polyhydric alcohol or polybasic acid was changed, and No. 8 and No.
, 9 shows examples in which the N group and the amount of the crosslinking monomer were changed. In addition, polyhydric alcohol and polybasic acid in the table indicate the ratio of each component in the polyester in mol%. Further, the composition ratio of the allyl ester resin and the crosslinkable monomer is expressed as ff[ffi%. Here, the allyl ester resin is obtained by allylating both ends of a polyester consisting of a polyhydric alcohol and a polybasic acid component.

Next, a method for producing a laminate using the resin composition for FF1-layer board will be described.

As a method for producing a laminate using the resin composition for laminates, for example, a base material is impregnated with the resin composition, a plurality of impregnated base materials are laminated, and a metal-clad VT laminate is produced. If this is the case, there is a method of stacking metal foils with or without adhesive applied to one or both sides of the metal foil, and then heating without pressure or under pressure to form the metal foil. At this time, the metal foil may be attached after the laminated impregnated base material is cured and formed.

As the above-mentioned base material, the same base materials conventionally used for laminates can be used, such as glass fiber cloth, glass nonwoven fabric, etc., cellulose fibers such as kraft paper, linter paper, etc. Examples include sheets or strips mainly made of paper and inorganic fibers such as asbestos.

When using paper as a base material, from the viewpoint of impregnability and quality,
Paper mainly composed of cellulose fibers, such as kraft paper, having an air-dried density of 0.3 to 0.7 g/cm' is preferred.

In addition, as a metal foil, electrolytic copper foil is commercially available for use in copper-clad laminates for electric circuits, and it is preferable to use this from the viewpoints of corrosion resistance, etching properties, and adhesive properties. However, the present invention is not limited to this. The metal foil preferably has a thickness of about 10 to 100 microns.

In order to effectively avoid bonding the metal foil and the base material, it is preferable to use an adhesive, and the adhesive is a liquid or semi-fluid adhesive that does not generate unnecessary side reaction products during the curing process. is preferred. Examples of such adhesives include acrylate adhesives, epoxy adhesives, epoxy acrylate adhesives, isocyanate adhesives, and various modified adhesives thereof.

The thickness of this laminate varies depending on the type of base material, the composition of the resin composition to be impregnated, and the purpose of the laminate, but is usually 0.5 to 5.
It is 1. Further, the proportion of the resin composition in the laminate is about 30 to 80 ffi%.

"Examples" Hereinafter, the resin composition for a laminate of the present invention and a laminate using this resin composition will be specifically explained using Examples, but the following Examples will limit the present invention. It's not a thing.

[Production of allyl ester resin (A)] 600 g of diallyl terephthalate and 78.4 g of ethylene glycol were placed in an IQ Mitsuro flask equipped with a distillation device.
g, dibutyltin oxide 0. Ig was charged and heated to 180°C under a nitrogen stream, and allyl alcohol produced was distilled off. When about 140 g of allyl alcohol had been distilled off, the pressure inside the flask was increased to 50 maHg to accelerate the distillation rate.

After the theoretical amount of allyl alcohol was distilled off, the reaction solution was heated to 1 aml while maintaining it at 200°C using a thin evaporator.
In g, unreacted diallyl terephthalate was distilled off. The reaction solution was poured into a vat, cooled, and pulverized to obtain a powdery allyl ester resin ([).

Further, allyl ester resins (n) to (V) were obtained using the same method as the method for obtaining the allyl ester tree R1 (1), except that the materials shown in Table 1 were used.

Table 2 shows the materials used and their blending amounts.

(Hereinafter referred to as "Kinpaku") (Examples 1 to 8) Kraft paper (manufactured by Tamako Paper Co., Ltd.) with a tsuboffi of 135 gem was soaked in an aqueous solution of Nikaresin S-305 (trade name, methylolmelamine manufactured by Nippon Carbide) and squeezed with a roller. It was dried at 120°C for 30 minutes.

There is methylolmelamine in the paper base material obtained! It was spread at 1.4% by weight. This paper is immersed in a resin solution containing 100 parts by weight of a resin composition consisting of an allyl ester resin (A) and a crosslinkable monomer (B) shown in Table 3, to which tifiU parts of each of benzoyl peroxide and dicumyl peroxide are added. Impregnated paper was obtained.

Eight sheets of the impregnated paper and adhesive-coated copper foil MK-61 (manufactured by Mitsui Mining and Mining Co., Ltd.) were stacked one on top of the other, and placed between two Lumirror films (manufactured by Toshi, polyester film) on top and bottom, and hot pressed using a scissor press. The heat and pressure conditions were 140°C for 10 minutes, and the pressure was 10
kg/cg+". After that, it was dried in a dryer to
It was heated at 0° C. for 1 hour to complete curing. The thickness of the copper-clad laminate thus obtained was 1.5 to 1.7 am.

The formulation of the resin composition for laminates, the measurement results of Tg of the cured product, and the measurement results of the electrical properties, heat resistance, and punchability of the copper-clad laminate obtained using this resin composition are summarized in the third section. Shown in the table.

(Comparative Examples 1-2) A copper-clad laminate was manufactured in the same manner as in Example 1.

Table 3 shows the formulation of the resin composition for laminates, the Tg of the cured product, and the measurement results of various properties of the copper-clad laminates.

(Conventional example) Phthalic anhydride, maleic anhydride, and diethylene glycol were used as a resin composition for a laminate, and the molar ratio of each component was 1.
Example I except that an unsaturated polyester resin containing 35% styrene synthesized at a ratio of 1:2 was used.
A copper-clad laminate was manufactured in the same manner as above. Table 3 shows the measurement results of the Tg of the cured product and various properties of the copper-clad laminate.

(Hereinafter, blank space) As is clear from Table 3, the laminates of the examples have excellent punching properties at temperatures near room temperature, and the laminates manufactured using the unsaturated polyester resin shown in the conventional example It has better heat resistance than a board. In addition, in the laminate shown in Comparative Example 1, the Tg of the cured product is higher than 90°C (therefore, the punching temperature is high, so when punching is performed at a temperature near room temperature, cracks are likely to occur in the punched part. On the other hand, in the case of the laminate shown in Comparative Example 3, the Tgh of the cured product was lower than 20° C. Therefore, when punching was performed at a temperature near room temperature, the area around the punched portion became white and the heat resistance was poor. The laminate shown in Comparative Example 2 had a high viscosity and impregnated the base material non-uniformly, making it impossible to measure.

The method for measuring the dielectric constant, dielectric loss tangent, and hot bending modulus in Table 3 is 1. This was done in accordance with JISC6481. Moreover, tracking resistance was measured by the IEC method. The measured values of dielectric constant and dielectric loss tangent are the values at I MHz, and the tracking resistance is the value measured at the adhesive surface.

Heat resistance is a laminate plate etched with copper foil at 260℃, 1
Visual inspection was performed after immersion in a solder bath for a minute.

The punchability was determined by the temperature at which 10 holes of 0.8 φ and 1.78 mm pitch could be punched without cracking. Further, the Tg of the cured resin product was measured using a thermal stress strain measuring device.

"Effects of the Invention" As explained above, the resin composition for laminates of the present invention has
40 to 95% by weight of an allyl ester resin (A) having an allyl ester group at the end of a polyester composed of a polybasic acid and a polyhydric alcohol, and 5 to 60% by weight of a radically polymerizable crosslinkable monomer (B). This resin composition for laminates is characterized in that the glass transition temperature (T g ) of the cured product is within the range of 20 to 90°C, so laminates can be manufactured using this resin composition. If you do,
A laminate can be manufactured without using the prepreg method, thereby reducing costs such as raw material costs and equipment costs, and also allowing the laminate to be manufactured through a simple process. Furthermore, the laminate manufactured using this resin composition for laminates satisfies punching characteristics at temperatures near room temperature without reducing heat resistance, mechanical properties, and electrical properties.

Claims (2)

[Claims] (1) 40 to 90% by weight of an allyl ester resin (A) having an allyl ester group at the end of a polyester composed of a polybasic acid and a polyhydric alcohol, and 5 to 90% by weight of a radically polymerizable liquid crosslinking monomer (B) 60% by weight, and the cured product thereof has a glass transition temperature of 20 to 90°C. (2) A laminate comprising the resin composition for a laminate according to claim (1) and a base material.