JPS6036384B2 - Manufacturing method for laminated products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a laminate used as a laminate for printed wiring.

Laminated boards for printed wiring are strongly required to be highly flame retardant.

In order to meet these demands, printed wiring laminates have been manufactured in the following manner. In other words, flame retardants such as halogen compounds and phosphorus compounds are added to the molding material, which is mainly composed of unsaturated polyester resin with good electrical properties and contains photopolymerization initiators, thermal polymerization initiators, etc., and then molded. A sheet-like body for the core layer is made, a reinforcing material such as glass cloth, non-woven fabric, or paper is layered on top of this, and then copper foil is layered on top of this, followed by heating and pressure molding. ■Hydrated alumina is used as a filler in a molding material that is mainly composed of unsaturated polyester resin and contains photopolymerization initiators, thermal polymerization initiators, etc. Molding in which hydrated alumina is used as a filler A printed wiring laminate is manufactured using the material. ■Make a molding material using unsaturated polyester resin containing flame-retardant components such as het acid and tetrabromo phthalic anhydride, and use this to manufacture printed laminates for granddaughter-in-law. However, each of these methods has the following problems. In other words, according to the method (■), halogen compounds, phosphorus compounds, etc. will be present in the laminate;
When the laminate is heated, they sublimate and decompose, which causes separation between the reinforcing material and the core layer, deteriorating the heat resistance of the laminate and lowering its electrical insulation. According to method (2), since hydrated alumina is present in the laminate, when the laminate is heated, water evaporates from the hydrated alumina, which causes separation between the reinforcing material and the core layer. The same problem as above arises. According to method (2), the unsaturated polyester resin used as the raw material for the molding material becomes sticky due to the flame retardant component, making it difficult to mold the molding material, which makes it difficult to manufacture the laminate. The problem arises. In view of these circumstances, the inventors set out to find a flame retardant that increases the flame retardancy of laminated products such as laminates without reducing their heat resistance or making manufacturing difficult. As a result of repeated research, it was discovered that brominated phenyl methacrylate ester and brominated phenyl acrylate ester have such properties.

As a result of further research, we found that when the above-mentioned retardant is incorporated into an unsaturated polyester resin sheet for the core layer, which starts curing when exposed to light and also when heated, a laminate product can be obtained. It was found that the curved fireworks were not flame retardant and the dimensional accuracy was improved. That is, since the above-mentioned unsaturated polyester resin sheet starts curing by light irradiation and heating, when a sheet-like material is layered on this sheet-like material and hot-press molded (thermo-press molding),
By subjecting the sheet-like body to at least one of light irradiation and heating prior to the hot-press molding to bring the sheet-like body into a semi-cured state, the amount of resin flowing out from the sheet-like body during hot-press molding can be reduced. do. As a result, the resulting laminate is not only flame retardant, but also has improved dimensional accuracy due to the reduced amount of resin flowing out. That is, the present invention is a method for manufacturing a laminate product by stacking a sheet-like material on a sheet-like material for a core layer mainly composed of an unsaturated polyester resin and heating and pressurizing the sheet-like material for the core layer. to the body,
As a flame retardant, brominated phenyl methacrylate ester represented by the following formula (in the formula, n is a positive integer of 1 to 5) and brominated phenyl acrylate ester represented by the following formula (in the formula, n is a positive integer of 1 to 5) The first gist thereof is a method for manufacturing a laminate product characterized by containing at least one of the following (an integer): By applying at least one of light irradiation and heating to a sheet-like material for use in a semi-hardened state, the sheet-like material is overlaid on this semi-hard I-Q state core-employed sheet-like material and heated and press-molded. A method for producing a laminate product, wherein a brominated phenyl methacrylate ester represented by the following formula (wherein n is a positive integer from 1 to 5) as a flame retardant is added to a sheet-like body for a core layer and the following formula: The second gist thereof is a method for manufacturing a laminate characterized by containing at least one of the following brominated phenylacrylic acid esters (wherein n is a positive integer of 1 to 5).

Next, this invention will be explained in detail.

The brominated phenyl methacrylate ester used as the bonito retardant in this invention is represented by the following formula (wherein n is a positive integer of 1 to 5). It is.

(In the formula, n is a positive integer of 1 to 5.) To produce a laminate according to the present invention, for example, first, one or both of the above-mentioned brominated phenyl methacrylate and brominated phenyl acrylate are contained, A sheet-like body for a core layer containing an unsaturated polyester resin as a main component is prepared.

As such a sheet-like body, one manufactured, for example, in the following manner is used. That is, an unsaturated polyester resin and additives such as an inorganic filler, a crosslinking agent, and a thermal polymerization initiator are appropriately combined, and the above-mentioned key fuel agent is added and mixed. A sheet-like body produced by extrusion into a sheet-like material having a thickness (for example, 0.5 to 5.0 mm) is used. In this case, as the inorganic filler, for example, those used in ordinary molding materials such as calcium carbonate, silica, clay, talc, and mica are used. As the crosslinking agent, for example,
Styrene, vinyl toluene, diallyl phthalate, methyl methacrylate, and ethylene glycol dimethacrylate are used, and as the thermal polymerization initiator, for example, benzoyl peroxide, t-butyl perbenzoate, dicumyl peroxide, etc. are used. Note that, if necessary, a polymerization inhibitor and reinforcing material (glass fiber, etc.) may be further used. It may be used in conjunction with the above-mentioned retardant (brominated phenyl methacrylate ester, frominated phenyl acrylate ester).

In particular, when used in combination with antimony oxide, the effect becomes even greater. In particular, the above-mentioned scale retardant is contained in the sheet-like body from 4 to 1 tsubo HR (PHR = parts by weight based on 10 parts by weight of the resin in the sheet-like body), antimony oxide is contained from 1 to tsubo HR, and the inorganic filler is contained at 50 tsubo HR. It is preferable to make it contain 200 PHR.

That is, the effect is maximized by selecting the above raw materials within the above range. Next, such a sheet-like body is overlaid with a sheet-like material and hot-press molded.

As the sheet material, glass cloth, nonwoven fabric, sheet reinforcing material such as paper, metal foil such as copper foil, prepreg, etc. are used. Usually, a sheet-like reinforcing material is layered on top of the sheet-like material, a metal foil is further layered on top of the sheet-like reinforcing material, and the sheet-like material is hot-pressed in this state. Note that prepreg may be directly stacked on the sheet-like body and hot-press molded in that state.
The method for producing a laminate by hot-pressing is the same as the known hot-pressing method in the present invention. In addition, a photopolymerization initiator is contained in the above-mentioned sheet-like body, and the resin in the sheet-like body is semi-cured by irradiating the sheet-like body with light (ultraviolet rays) prior to the above-mentioned hot-press molding. By doing this, if the sheet-like body is kept in a semi-cured state, there will be almost no loss of resin from the sheet-like body during hot-press molding, and the dimensional accuracy of the laminate product will be greatly improved.

Further, the same effect can be obtained even if the resin in the sheet-like body is semi-cured by heating instead of light irradiation. In this case, as mentioned above, there is no need to use a photopolymerization initiator. Note that the object of the present invention is not limited to printed wiring laminates, but may also be other laminates, laminate tubes, laminates, and other laminates. Next, examples of the present invention will be described together with comparative examples.

[Example 1] In a reaction vessel, 0.95 mol of ethylene glycol, 1.0 mol of propylene glycol, 0.5 mol of dimethyl terephthalate, and zinc acetate as a transesterification catalyst were added to a total of 0.
0.05% by weight, 190 in the presence of nitrogen gas
The transesterification reaction was carried out at ℃ for 5 hours.

Next, 0.5 mol of fumaric acid was added to this and esterification reaction was carried out at 200°C for 7 hours to obtain an unsaturated polyester resin having a softening temperature of 87q0. Next, 100 parts by weight (hereinafter referred to as "parts") of this unsaturated polyester resin, 1 part of diallyl phthalate, 1 part of dicumyl peroxide, 0.5 part of benzoin, 7 parts of tribromphenyl methacrylate, 2 parts antimony trioxide and 1 part clay
00 parts were kneaded in a pressure kneader, and then extruded from an extruder to obtain a sheet-like product with a low width and a thickness of 1.5 mm. Next, the above sheet-shaped body was irradiated with ultraviolet rays using an 80 W mercury lamp for a period of time shown in the table below to semi-cure the resin in the sheet-shaped body. Next, prepreg (glass cloth mixed with epoxy resin) was layered on the front and back sides of this semi-cured sheet material, and 170 qo, 3
A laminate was obtained by hot pressing under the conditions of 0k9/ground. [Example 2] 100 parts of an unsaturated polyester resin synthesized in the same manner as in Example 1, 8 parts of styrene, 1 part of t-butylperpenzoate, 0.6 part of benzene ethyl ether, and tribromphenyl. 9 parts of acrylic acid ester, 2 parts of antimony trioxide, 7 parts of silica powder, and 12 parts of glass fiber were mixed in a pressure kneader.

Thereafter, a laminate was obtained in the same manner as in Example 1, except that the irradiation time of the ultraviolet rays to the sheet-like body was changed as shown in the following table. [Example 3] 100 parts of an unsaturated polyester resin synthesized in the same manner as in Example 1, 1 part of dicumyl peroxide, 0.8 part of benzinisopropyl ether, and tribromphenyl methacrylate ester. 15 parts and 12 parts of calcium carbonate were kneaded with a roll.

From this point on, a laminate was obtained in the same manner as in Example 1 except that the ultraviolet irradiation time was changed as shown in the following table. [Comparative example 1]
100 parts of unsaturated polyester resin synthesized in the same manner as in Example 1, 1 part of styrene, 1 part of dicumyl peroxide
0.7 parts of benzoin methyl ether and 18 parts of hydrated alumina were mixed in a kneader.

From this point on, a laminate was obtained in the same manner as in Example 1 except that the ultraviolet irradiation time was changed as shown in the following table. [Comparative example 2]
100 parts of unsaturated polyester resin synthesized in the same manner as in Example 1, 10 parts of diallyl phthalate, t-butyl per-
1 part of penzoate, 0.5 parts of benzoin, 8 parts of hexabromobenzene, 2 parts of antimony trioxide, and 12 parts of calcium carbonate were mixed in a pressure kneader.

From this point on, a laminate was obtained in the same manner as in Example 1 except that the ultraviolet irradiation time was changed as shown in the following table. [Comparative Example 3] 0.95 mol of ethylene glycol, 1.0 mol of propylene glycol, 0.5 mol of tetrabromophthalic anhydride, and 0.5 mol of maleic anhydride were charged into a reaction vessel, and ester was prepared in the presence of nitrogen gas. An unsaturated polyester resin having a softening temperature of 85q0 was obtained.

Next, 10 parts of the unsaturated polyester resin described above, 1 part of diallyl phthalate, 1 part of dicumyl peroxide, 0 to 6 parts of benzoin ethyl ether, and 10 parts of silica powder were kneaded in a pressure kneader. From this point on, a laminate was obtained in the same manner as in Example 1 except that the ultraviolet irradiation time was changed as shown in the following table. The extrusion moldability of the sheet-shaped bodies, the ultraviolet irradiation time for the sheet-shaped bodies, and the heat resistance and insulation resistance of the obtained laminates in the above Examples and Comparative Examples are also shown in the following table.

(Note) The ultraviolet irradiation time is expressed as the charge during irradiation using an 80W mercury lamp, which is necessary to prevent the resin in the sheet from flowing during hot press molding at 1700C and 30k9/m.

Incidentally, when a flame retardancy test was conducted on the semi-cured sheet-like bodies obtained in the above Examples and Comparative Examples, all were found to be good under UL standard V-0. In addition, a sheet-like body was made in the same manner as in the above Examples and Comparative Examples, and a prepreg (same as that in the Examples and Comparative Examples) was directly stacked on this without irradiation with ultraviolet rays, and a sheet was obtained by hot-pressing. The laminate also showed substantially the same performance as the laminates obtained in the above Examples and Comparative Examples.

Claims (1)

[Scope of Claims] 1. A method for manufacturing a laminate product by stacking sheet-like materials on a sheet-like material for a core layer containing an unsaturated polyester resin as a main component and heating and pressurizing the sheet-like material for the core layer, the method comprising: a sheet for the core layer; Brominated phenyl methacrylate ester shown as a flame retardant in the form of a flame retardant ▲ There are mathematical formulas, chemical formulas, tables, etc. A method for producing a laminate product characterized by containing at least one of phenyl acrylic acid ester (numerical formula, chemical formula, table, etc.) (in the formula, n is a positive integer from 1 to 5). 2. The laminate product according to claim 1, wherein the sheet-like body for the core layer contains at least one of the brominated phenyl methacrylate and the brominated phenyl acrylate and antimony oxide. Manufacturing method. 3. The sheet-like material is a sheet-like reinforcing material and a metal foil, and the sheet-like material is stacked on the sheet-like material for the core layer, and the sheet-like reinforcing material and the metal foil are placed on the sheet-like material for the core layer. A method for manufacturing a laminate product according to claim 1 or 2, which is carried out by sequentially stacking layers. 4 A sheet-like material for a core layer, which is mainly composed of an unsaturated polyester resin and which starts curing even when exposed to light and also starts curing when heated, is subjected to at least one of light irradiation and heating to a semi-cured state. This is a method of manufacturing a laminate by stacking a sheet-like material on this semi-cured sheet-like material for the core layer and molding it under heat and pressure. Brominated phenyl methacrylate ester represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (in the formula, n is a positive integer from 1 to 5) and brominated phenyl acrylate ester represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, n is a positive integer from 1 to 5) A method for producing a laminate product characterized by containing at least one of the following. 5. The laminate product according to claim 4, wherein the sheet-like body for the core layer contains at least one of the brominated phenyl methacrylate and the brominated phenyl acrylate and antimony oxide. Manufacturing method. 6 The sheet-like material is a sheet-like reinforcing material and a metal foil, and the sheet-like material is stacked on the sheet-like body for the core layer, and the sheet-like reinforcing material and the metal foil are placed on the sheet-like body for the core layer. A method for manufacturing a laminate product according to claim 4 or 5, which is carried out by sequentially stacking layers. 7. The method for producing a laminate product according to claim 4, 5, or 6, wherein the sheet material for the core layer contains a photopolymerization initiator and a thermal polymerization initiator.