JPS6055284B2 - Manufacturing method of laminates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing laminates, particularly unsaturated polyester resin laminates.

BACKGROUND ART Conventionally, it has been widely known to manufacture laminates using prepregs that are not sticky at room temperature.

Generally, such prepregs that are not sticky at room temperature are circular unsaturated polyesters consisting of circular amorphous unsaturated polyesters and circular copolymerizable monomers and/or copolymerizable prepolymers. A composition is prepared by blending the resin with a solvent such as acetone or toluene, a polymerization inhibitor, a filler, a flame retardant, a thickener, a mold release agent, and other additives, and this composition is impregnated into a fibrous base material. Some products are manufactured by volatilizing a solvent under heating. In this case, it is necessary to use expensive circular copolymerizable monomers or prepolymers at room temperature, and solvents such as acetone and toluene are used during production, which not only complicates the process but also makes the production environment I didn't like it from any point of view.
Instead of such prepreg, as an unsaturated polyester resin, an unsaturated polyester resin consisting mainly of crystalline unsaturated polyester is dissolved in a normal liquid copolymerizable monomer such as styrene under heating, and a circle at room temperature is used. There is a prepreg using unsaturated polyester resin. By the way, in order to industrially manufacture large quantities of laminates using these prepregs, molding machines such as multi-stage presses are generally used, and these molding machines use conventional prepregs that do not have adhesive properties at room temperature. Without the use of a mold or spacer, the resin would flow out during pressurization and heating, making it impossible to obtain a laminate with a beautiful appearance.

The present inventors have investigated various ways to manufacture laminates with excellent appearance without using molds or spacers using currently used molding machines such as multi-stage presses and general presses. When heated under a pressure equal to or lower than the contact pressure and then integrated by heat molding, a prepreg containing woven fabric, long fiber nonwoven fabric, or filament mat as a fibrous base material of 20 to 6% by weight based on the prepreg can be obtained. The inventors have discovered that the intended purpose can be achieved by using the following, and have arrived at the present invention.

That is, the present invention involves heating an unsaturated polyester resin that is solid at room temperature and consisting of 40 to 9 parts by weight of an unsaturated polyester mainly composed of crystalline unsaturated polyester and 60 parts by weight of a liquid copolymerizable monomer. Manufacture of a laminate, characterized in that prepreg, which is non-tacky at room temperature and obtained by impregnating a fibrous base material, is heated under a pressure below the contact pressure, and then heated under pressure to be integrally molded. It is the law. According to the present invention, a laminate with a beautiful appearance can be obtained without the resin flowing out from the fibrous base material due to heat and pressure without using a mold or spacer.

Furthermore, the laminate of the present invention has particularly excellent electrical properties. In the present invention, as an unsaturated polyester resin that is solid at room temperature, an unsaturated polyester resin consisting of 40 to 9 parts by weight of an unsaturated polyester mainly consisting of crystalline unsaturated polyester and 60 to 1 part by weight of a liquid copolymerizable monomer is used. Since it is a polyester resin, there is no need to use expensive copolymerizable monomers or prepolymers that are solid at room temperature in the prepreg manufacturing stage, and there is no need to use solvents, resulting in lower raw material costs and manufacturing costs. Not only is it advantageous, but it is also extremely favorable in terms of the working environment. be.

The unsaturated polyester resin that is solid at room temperature used in the present invention is prepared by heating an unsaturated polyester mainly consisting of crystalline unsaturated polyester to a common liquid copolymerizable monomer such as styrene. There are also those obtained by dissolving the polyester in a solid state at room temperature, and those composed of an amorphous unsaturated polyester that is solid at room temperature and a copolymerizable monomer and/or copolymerizable prepolymer that is solid at room temperature. The former unsaturated polyester resin, which is solid at room temperature, is particularly preferred. Next, the former resin will be explained in detail. The crystalline unsaturated polyester used in the present invention is an unsaturated polyester produced using as raw materials a dicarboxylic acid or a functional derivative thereof having a symmetrical molecular structure and a diol also having a symmetrical molecular structure.

As a specific example, dicarboxylic acid raw materials include terephthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, lower alkyl esters or chlorides thereof, etc. Ethylene glycol as a diol raw material , 1,8-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-butene, 1,4-diol, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, 1,4-bis(2-hydroxyethoxy)cyclohexane, 1,4-bis(2-hydroxypropoxy)cyclohexane, 1,4-bis(2-hydroxyethoxy)benzene, 1,4 - Symmetrical diols such as bis(2-hydroxypropoxy)benzene and baraxylylene glycol.As long as the crystallinity of the unsaturated polyester is not significantly impaired, it has the above-mentioned symmetrical molecular structure. Along with the raw materials, small amounts of raw materials used in the production of amorphous unsaturated polyesters to give conventional liquid unsaturated polyester resins can be used. Such raw materials include orthophthalic acid, isophthalic acid, tetrachloro and tetrabromo ortho Phthalic acid, succinic acid,
Dicarboxylic acids such as adipic acid and dodecanedicarboxylic acid and their functional derivatives, and 1,2-dicarboxylic acid, diethylene glycol, dipropylene glycol, 1,8-butanediol, 2,2,4-trimethyl-1, 3-pentanediol, bisphenols,
Examples include diol raw materials such as ethylene oxide and propylene oxide adducts of hydrogenated bisphenols and halogenated bisphenols.
The general amount of these raw materials used in combination is 20 mol % or less of the total dicarboxylic acid component for the dicarboxylic acid component, and 40 mol % or less of the total diol component for the diol component.
Two or more kinds of crystalline unsaturated polyesters can be used in combination.

A normal amorphous unsaturated polyester can also be used in combination with the crystalline unsaturated polyester within a range that does not impair the solidity of the unsaturated polyester resin at room temperature.

The proportion in which they are used together varies depending on the degree of crystallinity of the crystalline unsaturated polyester, the type and amount of the copolymerizable monomer, etc., but it is necessary to maintain the solidity of the unsaturated polyester resin at room temperature. , it is desirable that the amount is 5% or less based on the total unsaturated polyester.

In this case, two or more types of amorphous unsaturated polyesters can be used together. Next, the liquid copolymerizable monomers used in the present invention include styrene monomers such as styrene, monochlorostyrene, t-butylstyrene, a-methylstyrene, vinyltoluene, divinylbenzene, diallyl Examples include allylic monomers such as phthalate, diallyl isophthalate, diallyl terephthalate, diallyl fumarate, and diallyl adipate, acrylic ester monomers such as methyl or ethyl acrylate and methyl or ethyl methacrylate, vinyl acetate, and dibutyl fumarate.

Two or more of these copolymerizable monomers can be used in combination.

The content of the copolymerizable monomer is 10 to 60% by weight of the unsaturated polyester resin.

If the blending amount exceeds the printing weight %, the solidity of the unsaturated polyester resin at room temperature will not be sufficient, and at the same time,
It has drawbacks such as not losing flow resistance during molding and poor moldability. Further, if the amount is less than 1% by weight α, the physical properties of the cured molded product will be poor and the unsaturated polyester resin will not be able to exhibit sufficient performance. The crystalline unsaturated polyester can be mixed with the copolymerizable monomer to form an unsaturated polyester resin that is solid at room temperature.

This mixing can be carried out by a screw type method such as a Panbury mixer, a pump blender, a kneader, or a high speed mixer, or by a stirring blade type method. The mixing is generally performed under heating. The unsaturated polyester resin used in the present invention, which is solid at room temperature, contains a polymerization catalyst, but the amount thereof is generally 0 parts per 10 parts of the unsaturated polyester resin.
．． It is contained in an amount of 3 to 3 parts by weight.

As the polymerization catalyst, a medium- or high-temperature decomposition type catalyst used for ordinary liquid unsaturated polyester resins may be used, but since the unsaturated polyester resin used in the present invention is solid at room temperature, unsaturated polyester resin or its When producing compositions or compositions containing fillers, pigments, flame retardants, thickeners, mold release agents, etc., it is necessary to knead them under heat in order to achieve sufficient mixing. It is necessary to select a catalyst that will not decompose under crosstalk conditions. Specific examples of such polymerization catalysts include methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, p-
Menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, A,a'-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2, 5-di(benzoylperoxy)hexane, 2
,5-dimethyl-2,5-di(t-butylperoxy)
Hexin-3, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, G-t -butyldiperoxyphthalate, t-butylperoxymaleic acid, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and the like.

The unsaturated polyester resin used in the present invention, which is solid at room temperature, contains a polymerization inhibitor if necessary to adjust the gelation time, but the content is generally 100 parts by weight of the unsaturated polyester resin. Target is 0.5
Contain less than part by weight.

As the polymerization inhibitor, those used for controlling the gelation time of ordinary unsaturated polyester resins may be used, and there are no particular limitations on the polymerization inhibitor. The method for adding the polymerization catalyst and polymerization inhibitor is generally to mix them at the time when the crystalline unsaturated polyester is dissolved in the copolymerizable monomer.

The unsaturated polyester resin that is solid at room temperature used in the present invention may include calcium carbonate, aluminum hydroxide, talc, clay, silica, calcium silicate, barium sulfate, magnesium carbonate, diatomaceous earth, silica sand, glass, powder, etc. , fillers such as glass flakes,
One or more flame retardants such as antimony trioxide, phosphorus compounds, and halogen compounds, thickeners such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, and mold release agents such as zinc stearate and calcium stearate. Compounding agents can be added.

The general method for blending the above compounding agents is to heat and knead the above compounding agents into a crystalline unsaturated polyester resin containing a polymerization catalyst and, if necessary, a polymerization inhibitor using a kneader, high-speed mixer, etc. be.

The woven fabric, long-fiber nonwoven fabric, or filament mat used as the fibrous base material in the present invention includes inorganic fibers such as glass and asbestos, natural fibers such as cotton yarn and rayon yarn, and polyamide, polyester, polyacrylonitrile,
Polyvinyl chloride, polyvinylidene chloride, polyethylene,
Those made from synthetic fibers such as polypropylene are preferred.

Woven fabrics include plain weave, twill weave, satin weave, open plain weave, and gauze weave, and long fiber nonwoven fabrics are manufactured using adhesives from spun bonds and filaments. There are non-woven fabrics that can be used. These woven fabrics, long-fiber nonwoven fabrics, or filament mats are available in a wide variety of combinations of weaving methods, counts used, densities, etc., and the optimal one can be used depending on the purpose. In addition, woven fabrics, long fiber non-woven fabrics or filamentous fabrics are also available. The filaments and mats may be used alone or in combination of two or more. As a woven fabric, the thickness is approximately 1.0
A woven fabric with a thickness of 0 m or less and a weight of about 500 y/d or less is used, and a woven fabric with a thickness of about 0.50 m or less and a weight of about 800 y/d or less is particularly preferred. On the other hand, as the long fiber 4 nonwoven fabric or filament mat, one with a thickness of about 1.50 wgn or less and a weight of about 300 y/d or less is used, particularly a thickness of about 1.007 m or less and a weight of about 200 g/d. The following are preferred. Generally speaking, the thinner the layer and the lighter the weight, the easier it is to use, but it becomes necessary to stack a large number of layers. It can be used in combination with a prepreg containing a fibrous base material other than the woven fabric, long-fiber nonwoven fabric, or filament mat used in the present invention, as long as it does not impair the moldability during lamination molding.

Examples of such fibrous base materials include linter paper, rayon paper, kraft paper, asbestos paper, short fiber nonwoven fabric, chinoyopto strand mat, and the like.
In the method of the present invention, a fibrous base material is first impregnated with an unsaturated polyester resin that is solid at room temperature or a resin composition containing additives as necessary, while maintaining fluidity under heating. A prepreg with no tackiness at room temperature is produced by allowing it to cool.

In this case, the content of the fibrous base material, in particular woven fabric, long fiber nonwoven fabric or filament mat in the prepreg, is approximately 20
It is particularly preferable that the amount of ruts be 6% to 6%.

If the content exceeds about 6%, not only will the adhesion between the prepregs not be sufficient when laminated, but the base material may become white or embossed. If the amount is less than about 2%, the function as a laminate will not be sufficient. Methods for impregnating fibrous substrates, especially woven fabrics, long-fiber nonwoven fabrics, or filament mats with resin, include squeeze method, contact method,
There are immersion-squeeze methods, immersion methods, coater methods, etc.
It is preferable to adopt a method that allows sufficient impregnation and defoaming. The prepreg thus obtained is dry at room temperature and has no tackiness.

In this case, the prepreg may be coated with a film of polyester, polypropylene, polyethylene, polybutadiene, polyvinylidene chloride, polyvinyl chloride, or the like. The method of the present invention then heats at least one sheet of prepreg to a pressure below the lap contact pressure.

The heating temperature and heating time in this case vary depending on the composition of the crystalline unsaturated polyester resin used for prepreg production, the composition of the composition, the type and amount of the polymerization catalyst and polymerization inhibitor contained, but generally speaking Specifically, the heating temperature is 70 to 200° C., and the heating time is several 1 to 2 to several 1 times. Next, the prepreg is heated under pressure to obtain a laminate. The pressure in this case is generally 10-200
k9/CFll, the heating temperature is 70 to 200°C, and the heating time is several minutes to several hours. Both the heating time under pressure below the contact pressure and the heating time under pressure become shorter as the heating temperature becomes higher. If heating is not carried out under a pressure lower than the contact pressure, the fibrous base material will whiten or emboss, and the adhesive strength between the laminated prepregs will be insufficient. If necessary, the obtained laminate may be post-treated by heating it to an arbitrary temperature under an arbitrary pressure or no pressure. The method of the present invention can be directly applied to the production of other laminated products other than laminated plates, such as laminated pipes, laminated tubes, laminated rods, and molded laminates.

The unsaturated polyester resin laminate obtained by the method of the present invention undergoes a secondary processing step and is used in fields such as electrical insulation materials and mechanical parts.

The present invention will be explained in more detail below using examples.

In the examples, "part" indicates part by weight, and "%" indicates weight %. Arc resistance and tracking resistance were each measured in accordance with ASTM D-495, IEC Pub, 112. Reference example (manufacture of unsaturated polyester) Terephthalic acid 1.00 (molar ratio) was placed in a stainless steel autoclave equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a partial condenser equipped with a thermometer.
Add 0.01 mol% of titanyl potassium acid and 0.03 mol% of triethylamine to 2.10 (molar ratio) of ethylene glycol and terephthalic acid, and under pressure of 3.0 kg/Cli, gauge pressure, 220 After reacting for 3 hours at a reaction temperature of ~230°C, the pressure was returned to normal pressure.

Next, 1.00 (molar ratio) of fumaric acid was added, and the mixture was heated under normal pressure.
The reaction was carried out at a reaction temperature of 205 to 210° C. under a nitrogen stream to obtain unsaturated polyester A having an acid value of 12. Next, unsaturated polyester B-1 was produced in the same manner as unsaturated polyester A using the raw materials shown in Table 1 below.

In Table 1, A-G are crystalline unsaturated polyesters,
H and I are amorphous unsaturated polyesters. In the table, the symbols indicate the following.

FA: Fumaric acid MA: Maleic anhydride TPA: Terephthalic acid IPA: Isophthalic acid EG: Ethylene glycol BG: 1,4-butanediol HG: 1,6-hexanediol PG: 1,2-propanediol Example 1 Crystallinity An unsaturated polyester resin is obtained by dissolving 70 parts of unsaturated polyester in 30 parts of styrene under heating, and then 0.0 parts of hydroquinone is dissolved under heating. The mixture was added with 1 part of t-butyl peroxybenzoate and mixed well, and then allowed to cool to room temperature to obtain a solid unsaturated polyester resin.

This unsaturated polyester resin was heated to maintain its fluidity and then made into a 50cm wide glass cloth [EHlOOl
After impregnating the prepreg with Nl (manufactured by Nippon Glass Fiber), the prepreg was allowed to cool to room temperature to obtain a prepreg with no stickiness at room temperature.

The glass content of this prepreg was about 45%. In exactly the same manner, various prepregs containing the above-mentioned glass cloths shown in Table 2 were obtained using the unsaturated polyester B-1 shown in Table 1.

None of the prepregs exhibited tackiness at room temperature, and each prepreg had a glass content of about 45%. The obtained prepreg is 50C each! fl×50
It was cut into pieces of cm, and one layer of the same prepreg was laminated.

Next, a polyethylene terephthalate (PET) film was placed on a press plate heated to 140°C, the laminated prepreg was placed on top of it, and the PET film was further placed on top of it, and the film was heated to 1.0 to 1.0°C under contact pressure. Intermittent heating followed by 100k9/C! A laminate was obtained by heating at 140° C. for 3 days under a pressure of 1 liter. The electrical properties of the various laminates thus obtained are shown in Table 2. For comparison, when heating under pressure immediately without heating under contact pressure, the glass
A laminate with a poor appearance, including marked whitening and embossment of the cloth, was obtained. Comparative Example Various unsaturated polyesters A-G that are not sticky at room temperature were used in the same manner as in Example 1, except that a 150 cm wide chopstick strand mat [EM3OO-G-1, manufactured by Nippon Glass Fiber] was used. Got prepreg.

The glass content of each prepreg was about 45%. The obtained prepregs were each cut to a size of 50 cm, and three sheets of the same prepreg were laminated.

Next, a laminate was molded in the same manner as in Example 1, but only a laminate with an extremely poor appearance due to significant resin flow from the glass substrate was obtained. Example 2 Part of crystalline unsaturated polyester D6O was dissolved in 40 parts of styrene under heating to obtain an unsaturated polyester resin, and further 0.0 parts of hydroquinone was dissolved. The mixture was added with 1 part of di-t-butyl peroxide and mixed well, and then allowed to cool to room temperature to obtain a solid unsaturated polyester resin.

This unsaturated polyester resin was impregnated into various 50 cm wide woven fabrics, long fiber nonwoven fabrics, and filament mats shown in Table 3 while maintaining fluidity under heating, and then allowed to cool to room temperature. A non-tacky prepreg was obtained.

The base material content of the prepreg was 45 to 50%. The obtained prepreg is 50cm x 50c7 each! The same prepreg was then cut into 5 to 1 layers.

Next, a PET film is placed on a press plate heated to 130°C, the laminated prepreg is placed on top of it, and then a PET film is placed on top of it, and then the press top plate and the PET film are placed.
Keeping the distance from the T film to about 1WrIn, 2.5 to 3
．． Heating the powder, then under pressure of 80k9/CFlf for 1
A laminate was obtained by heating at 30'C for 40 minutes. The electrical properties of the various laminates obtained are shown in Table 3. For comparison,
When heating was performed immediately under pressure without heating while keeping the distance between the upper plate of the breather and the PET film at about 1w0n, a laminate with a poor appearance due to whitening and embossment of the base material was obtained. Comparative Example 2 50cm wide tip ●Strand ●Mat [CM4
A prepreg with no stickiness at room temperature was obtained in the same manner as in Example 2, except that 5OAl (manufactured by Nittobo) was used.

The glass content was approximately 50%. This prepreg is 5
After cutting to 0 cm x 50 cm and laminating two sheets, a laminate was molded in the same manner as in Example 2, but only a laminate with extremely poor appearance was obtained, with significant resin flow from the glass base material. . Example 3 In exactly the same manner as in Example 1, prepregs containing various woven fabrics, long fiber nonwoven fabrics, and filament mats shown in Table 4 were obtained from the unsaturated polyesters shown in Table 4.

Each of the obtained prepregs is 50Crr1×50cm
and laminated as shown in Table 4.

Next, the PET film was placed on a press plate heated to 140°C, the laminated prepreg was placed on top of the PET film, and the PET film was further placed on top of it, and then the PET film was heated to 1.0°C under contact pressure.
~1. Heating the powder, then heating the powder at 140'C under a pressure of 80k9/Clt, and then increasing the heating temperature to 160°C.
The mixture was heated to 100 ml. The electrical properties of the obtained laminate are shown in Table 4. For comparison, when heating was not performed under contact but immediately under pressure, a laminate with poor appearance with significant whitening and embossment of the base material was obtained.

Example 4 A crystalline unsaturated polyester C6O part was dissolved in 40 parts of styrene under heating to obtain an unsaturated polyester resin, and further 0.0% of hydroquinone was dissolved. The mixture was added with 1 part of dicumyl peroxide and mixed well, and then allowed to cool to room temperature to obtain a solid unsaturated polyester resin.

Calcium carbonate [N
40 parts of S2OO, manufactured by Nitto Funka Kogyo Co., Ltd.] were added thereto and thoroughly mixed using a high-speed mixer while heating to obtain an unsaturated polyester resin composition 2 that was solid at room temperature. This unsaturated polyester resin composition was impregnated into a 50 cm wide glass cloth [EMH25O3N (described above)] while maintaining its fluidity under heating, and then allowed to cool to room temperature to form a prepreg with no stickiness at room temperature. I got 3.

The glass content of this prepreg was about 50%. In exactly the same manner, unsaturated polyester resin B-1 in Table 1
Using this method, glass cloth-containing prepregs shown in Table 5 were obtained.

5 Each obtained prepreg is 50cm x 50C7! The same prepreg was cut and laminated once. Next, PE was placed on a press plate heated to 130°C.
4. After laying the T film, placing the laminated prepreg on top of it, and then layering the PET film on top of that, the gap between the upper plate of the breather and the PET film was set to about 1 inch.2.
5-3. The powder was heated for one powder, then heated for one powder at 130'C under a pressure of 100 kg/Clt, then the heating temperature was increased to 160°C for three powders, and further heated for three powders at 160°C.

Claims (1)

[Scope of Claims] 1. A solid unsaturated polyester resin at room temperature consisting of 40 to 90 parts by weight of an unsaturated polyester mainly consisting of crystalline unsaturated polyester and 60 to 10 parts by weight of a liquid copolymerizable monomer is heated. A laminate characterized in that a prepreg, which is non-tacky at room temperature and is obtained by impregnating a fibrous base material underneath, is first heated under a pressure below the contact pressure, and then heated under pressure to be integrally molded. Manufacturing method. 2. The prepreg, which is non-tacky at room temperature, contains 20 to 60 parts by weight of woven fabric, long-fiber nonwoven fabric, or filament mat as a fibrous base material, based on the prepreg. Method of manufacturing laminates.