JPS6345699B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention particularly relates to a cellulose-based unsaturated polyester resin electrical laminate having excellent punching workability and moisture resistance, and a method for producing the same. The electrical laminate used in the present invention refers to a laminate or a metal foil-covered laminate used as a substrate for various electronic components, for example, and its shape is a plate-like material with a thickness of approximately 0.5 to 5 mm. say. The above-mentioned laminate is manufactured by impregnating a cellulose base material with an unsaturated polyester resin, then laminating and curing the impregnated cellulose base material. For example, the present inventors have already proposed a method for continuously manufacturing electrical laminates using unsaturated polyester resin, which is liquid at room temperature, in JP-A-55-4838, JP-A-55-53013, etc. There is. In addition, as an example of manufacturing a laminate by heat and pressure molding using an unsaturated polyester resin that is solid at room temperature, Japanese Patent Publication No. 48-29625,
There are many proposals such as JP-A-51-111885 and JP-A-52-92288, but these have not yet reached the stage of practical application. Cellulose-based unsaturated polyester resin laminates obtained by the above method have extremely good electrical insulation properties, soldering heat resistance, mechanical strength, etc. under normal conditions, but due to moisture absorption, these laminates cannot be used as electrical laminates. It has the disadvantage that the deterioration of characteristics is often large. Although the unsaturated polyester resin itself has excellent electrical insulation, heat resistance, and moisture resistance, it has poor adhesion to the cellulose that makes up the base material, and the interface between the resin and cellulose fibers peels off due to moisture absorption. This is thought to be due to the fact that the amount of moisture absorbed increases accordingly, leading to a decrease in various performances. As an attempt to improve these drawbacks, a method has already been proposed in which a cellulose base material is treated with an initial condensate of an amino resin organic compound (Japanese Patent Publication No. 13781/1981). By the way, the present inventors also pre-treated a paper base material with the above-mentioned initial condensate of the amino-based organic compound, created a laminate from it and an unsaturated polyester resin, and investigated its performance, and found that no pre-treatment was performed. Compared to conventional cases, there is less deterioration in electrical insulation properties and soldering heat resistance due to moisture absorption, and a considerable improvement can be seen in terms of moisture resistance and water resistance. The punching workability was not at all practical.
It is believed that the punching processability is greatly influenced by the physical properties of the unsaturated polyester resin used, and the present inventor used paper that had undergone the above-mentioned pretreatment and examined a large number of unsaturated polyester resins on the market. However, there were none that had good punching workability and were of practical use. In view of the current situation, the present inventors conducted intensive research and found that (a) melamine resin and/or guanamine resin, (b)
A mixture or condensation product of one or more resins selected from urea resins, cyclic urea resins, and phenolic resins (hereinafter referred to as (a) and/or (b))
In order to impart flexibility to resins represented by (sometimes referred to as amino resins in the present invention), groups such as hydroxyl groups, carboxyl groups, amino groups, and amide groups that can be condensed with methylol groups are added to the molecule. The present inventors have discovered that by mixing or condensing one or more higher aliphatic derivatives (c), the resulting laminate has excellent punching workability and moisture resistance, and has completed the present invention. . The present invention will be explained in detail below. In the present invention, (a) melamine resin and guanamine resin refer to initial condensates of formaldehyde and melamine or guanamines such as formoguanamine, acetoguanamine, propioguanamine, benzoguanamine, and adipodiguanamine, or their methylol groups. It refers to something partially or completely etherified with a lower alcohol such as methanol or butanol. The urea resin of the resin shown in (b) refers to the initial condensation product of urea and formaldehyde, and examples of the cyclic urea resin include ethylene urea resin, propylene urea resin, triazone type resin, uron resin, glyoxal resin, etc. can be given. Furthermore, the phenolic resin refers to a so-called resol type phenol formaldehyde resin obtained by condensing phenols such as phenol, cresol, xylenol, alkyl-substituted phenols, and polyphenols with formaldehyde under an alkali catalyst. Examples of higher aliphatic derivatives (c) that are mixed or condensed with the resins (a) and (b) above for the purpose of improving punching workability include the following. That is,
Saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid; unsaturated fatty acids such as oleic acid, erucic acid, linoleic acid, eleostearic acid, linolenic acid, and the above fatty acids. ethylene glycol, polyethylene glycol, propylene glycol,
Esters with polyhydric alcohols such as glycerin, pentaerythritol, and sorbitol, aliphatic amides which are derivatives of fatty acids such as those mentioned above, and caprylic alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, etc. Examples include saturated or unsaturated higher alcohols, ethers of higher alcohols and polyhydric alcohols, and aliphatic amines that are derivatives of higher alcohols. Also, oxyfatty acids and derivatives thereof such as ricinoleic acid can be used for the same purpose. In short, it is possible to have in the molecule a group that can condense with the methylol group of the amino resin, such as a hydroxyl group, carboxyl group, amino group, or amide group, and a long-chain alkyl group that acts to weaken the cohesive force of the amino resin. This is a necessary condition as a punching processability modifier. The number of higher aliphatic derivatives that meet these conditions is extremely large, but according to the results of studies conducted by the present inventors, when the number of carbon atoms is 8 or more, they can be used as punching processability modifiers. The effect of oleic acid, oleyl alcohol, and their derivatives, such as oleic acid monoglyceride, oleic acid diglyceride, oleic acid amide, and oleylamine, which have 18 carbon atoms and one unsaturated group, or a mixture of two or more of them was used. It has also become clear that the performance of the resulting laminate is well-balanced and good, and that it is a preferred embodiment of the present invention. By the way, the optimum amount of such a modifier to be used differs depending on the glass transition temperature of the unsaturated polyester resin used in the laminate, but it is usually used for (a) melamine resin and/or guanamine resin, and (b) ) A range of 3 to 40 parts by weight per 100 parts by weight of an amino resin consisting of one or a mixture or condensation product of one or more resins selected from urea resins, cyclic urea resins, and phenolic resins. Inside is preferable. If the amount of the modifier used is less than 3 parts by weight, the effect of improving punching workability will be small, and if it exceeds 40 parts by weight, mechanical strength, heat resistance, etc. will decrease when made into a laminate. big. The method for using it may be either by mixing the modifier and the above amino resin in the form of a solution or suspension, or by condensing the two in advance. . In this case, water, alcohols, ketones, esters, etc. are used as the solvent. In addition, the concentration of these treatment agents should be adjusted so that the total amount deposited on the cellulose fiber base material after drying is 3 to 30 parts by weight, preferably 6 to 20 parts by weight, based on the weight of the dry base material. is desirable; if the amount is less than 3 parts by weight, the effect will not be sufficient; if it exceeds 30 parts by weight, the plate will become brittle when made into a laminate and the punching workability will deteriorate. A solution or suspension of the treatment agent prepared under the above conditions is coated with a cellulose paper base such as kraft paper or linter paper, or in some cases a cellulose yarn fabric base such as cotton or rayon, using a dipping bath, roll coater or After impregnation using a spray or the like, a treated substrate is obtained by drying to remove the solvent. The desirable drying temperature is usually 50 to 170°C, and the drying time is about 0.5 to 60 minutes. On the other hand, in the unsaturated polyester resin used in the present invention, the structural formula of the unsaturated polyester is, for example, Generally well-known polyols can be used as raw materials, such as ethylene glycol, propylene glycol, diethylene glycol, 1.4-butanediol and 1.5-pentanediol, bisphenol A-propylene oxide adduct saturated polybasic. Phthalic anhydride as acid,
Isophthalic acid, terephthalic acid, adipic acid, sebacic acid, azelaic acid, unsaturated polybasic acids such as maleic anhydride and fumaric acid are common, and are a mixture of these and a crosslinking monomer. . Furthermore, a mixture of an epoxy-acrylate having two or more acryloyl groups or methacryloyl groups at the molecular end and a crosslinking monomer, which is generally called a vinyl ester resin, can also be used in the present invention. Styrene is commonly used as a crosslinking monomer, but other examples include α-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, alkyl acrylates having 1 to 10 carbon atoms, alkyl methacrylates having 1 to 10 carbon atoms, and phthalic acid. Monomers such as diallyl and triallyl cyanurate can also be used. The amount of these crosslinking monomers used is
20-50% by weight of unsaturated polyester resin,
Furthermore, a general-purpose organic peroxide is added as a curing catalyst, and a curing accelerator is added as necessary during curing. In addition, the curing catalyst is not limited to these,
All known curing catalysts such as light-sensitive curing catalysts and radiation-sensitive curing catalysts can be used together with organic peroxides or alone. Further, ultraviolet absorbers, polymerization inhibitors, colorants, cure shrinkage inhibitors, fillers, etc. may be added as necessary. An electrical laminate can be produced by impregnating the treated base material with the unsaturated polyester resin liquid, laminating the resin-impregnated base materials, and curing the resin-impregnated base materials. At this time, the unsaturated polyester resin is preferably liquid at room temperature, and has a viscosity of 0.1 to 30 poise, more preferably 0.5 to 15 poise. Furthermore, there is no restriction on the molding pressure when laminating and curing base materials impregnated with unsaturated polyester resin, but the present inventors have already reported that
As proposed in 2007, superior performance laminates can be obtained by curing under substantially no pressure, which is a preferred embodiment of the present invention. Note that the punching workability of the laminate obtained from the treated base material of the present invention is excellent, but in order to make low-temperature punching workability possible, the glass transition temperature of the cured product of the unsaturated polyester resin must be 20 It is preferable to use resins at ~80°C. The laminates and metal foil-clad laminates produced by the above method have excellent punching workability and moisture resistance, and can be used as electrical laminates for various purposes such as printed circuit boards. Next, the present invention will be explained in more detail with reference to Examples. Example 1 12 parts of melamine-urea cocondensation resin (Showa Kobunshi, Polyfix PM-138) and oleic acid mono-diglyceride (Kao Soap, Atmos 300) were added to 100 parts by weight (hereinafter abbreviated as parts) of water. 50%
Prepare a processing solution from 4 parts of emulsion, and
A piece of kraft paper with a thickness of 285 μm was immersed, taken out, and the excess treatment liquid was squeezed out using a roll, followed by drying at 120° C. for 20 minutes to obtain treated paper with a coating weight of 13.7%. On the other hand, using diethylene glycol, isophthalic acid, and maleic anhydride as raw materials, the molar ratio of each raw material component is 3:2:1, and the average molecular weight is approximately
3900, and 1 part of Perhexa 3M (manufactured by NOF Corporation) was added as a curing catalyst to a resin liquid consisting of 62 parts of unsaturated polyester and 38 parts of styrene condensed by a conventional method. This resin solution was impregnated into the above-mentioned treated paper, five sheets were laminated, and at the same time, a 35μm electrolytic copper foil coated with epoxy adhesive was laminated, and the resin was cured at 100℃ for 45 minutes to form a 1.6mm thick copper-clad laminate. Got the board. The performance is shown in Table 1. Example 2 100 parts of benzoguanamine, 85 parts of phenol, 37
190 parts of formalin and 5 parts of diethylamine were reacted under reflux for 1 hour in a three-necked flask equipped with a stirrer and a reflux condenser, and after dehydration under reduced pressure, methanol was added.
300 parts were added to obtain a methanol solution of benzoguanamine/phenol cocondensation resin. This solution 16
1 part, 2 parts of oleic acid monoglyceride (Riken Vitamin Oil, Rikemar OL-100) and 100 parts of methanol.
This was used as a processing solution. This treatment liquid has a thickness of
A piece of 285μ kraft paper was immersed, the excess liquid was squeezed out using a roll, and the mixture was dried to obtain treated paper with a coating weight of 14.9%. From this treated paper, 1.6
A copper-clad laminate of mm was obtained. This performance is shown in Table 1. Comparison Example 16 parts of the methanol solution of the benzoguanamine/phenol cocondensation resin obtained in Example 2 was added to 100 parts of methanol to prepare a treatment liquid, and a treated paper with a coating weight of 12.5% was obtained in the same manner as in Example 2. Subsequently, a 1.6 mm copper-clad laminate was produced in the same manner as in Example 2. Its performance is shown in Table 1.

[Table] Punching workability is ASTM-D617, water absorption rate is JIS-
Based on C6481.

Claims (1)

[Scope of Claims] 1. An electrical laminate comprising a cellulose base material and an unsaturated polyester resin, wherein the cellulose base material is (a) a melamine resin and/or a guanamine resin, (b) a urea resin, a cyclic urea resin. , one or more resins selected from phenolic resins,
(c) After pre-impregnation treatment with a mixture or condensation product of higher aliphatic derivatives having at least one group in the molecule that can be condensed with the methylol group in the resins (a) and (b) above. An unsaturated polyester resin electrical laminate made by impregnating, laminating, and curing unsaturated polyester resin. 2. The laminate according to claim 1, wherein the group capable of condensation with a methylol group is a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an amide group. 3. The higher aliphatic derivative having at least one group capable of condensation with a methylol group is oleyl alcohol,
The laminate according to claim 1, which is one or a mixture of two or more selected from the group consisting of oleic acid, oleic acid monoglymolide, oleic acid diglyceride, oleic acid amide, and oleylamine. 4. The laminate according to claim 1, wherein the unsaturated polyester resin has a cured product having a glass transition temperature of 20 to 80°C. 5 The cellulose base material is made of (a) melamine resin and/or guanamine resin, (b) urea resin, cyclic urea resin,
One or two selected from phenolic resins
and (c) a higher aliphatic derivative having at least one group in its molecule that can be condensed with the methylol group in the resins (a) and (b) above. , After taking it out, heat and dry it,
A method for producing an unsaturated polyester resin electrical laminate, characterized in that the treated cellulose base material is impregnated with an unsaturated polyester resin liquid, then laminated and cured under substantially no pressure conditions. 6. The method according to claim 5, wherein the group capable of condensation with a methylol group is a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an amide group. 7 The higher aliphatic derivative having at least one group capable of condensation with a methylol group is oleyl alcohol,
The method according to claim 5, which is one or a mixture of two or more selected from the group consisting of oleic acid, oleic acid monoglyceride, oleic acid diglyceride, oleic acid amide, and oleylamine. 8. The manufacturing method according to claim 5, wherein the unsaturated polyester resin has a cured product having a glass transition temperature of 20 to 80°C.