JP4595429B2 - Laminated board for printed wiring board mounting LED - Google Patents

Description

  The present invention relates to an electrical composite white laminate on which light emitting components are mounted.

  In recent years, electronic devices using light emitting diodes such as white and blue are rapidly increasing in mobile phones, lighting devices, light emitting units of game machines and game machines, and the like. As such a light emitting diode, a chip LED has come to be used with the downsizing and thinning of electronic equipment.

Here, as the printed wiring board on which the chip LED is mounted, titanium oxide is conventionally thermosetting in order to have heat resistance and water resistance and to increase the reflectance in the visible short wavelength region such as white and blue. A white substrate contained in a resin is used (for example, Patent Document 1).
JP 2003-152295 A

  However, in a conventional printed wiring board using a white substrate, when titanium oxide is contained in a thermosetting resin, a phenomenon occurs in which the substrate gradually discolors due to heat generated from the LED during use and the luminance decreases. This has been a problem especially when using chip LEDs.

  The present invention has been made in view of the above points, and it is an object of the present invention to provide an electrical composite white laminate with less discoloration of the substrate due to the heat generated by the LED and less reduction in luminance.

As a result of intensive studies to solve the above problems, the inventors have determined that the thermosetting resin constituting the white laminate is a radical polymerizable resin (a) , a thermoplastic resin (b) , a radical polymerizable monomer (c), Comprising an antioxidant (d) and an inorganic filler (e) , the substrate can be made white opaque by forming a sea-island structure with a radical polymerizable resin and a thermoplastic resin when the resin is cured; and It has been found that by adding an antioxidant, heating discoloration of the substrate due to heat generation of the LED can be prevented, and the present invention has been made. Here, the radical polymerizable resin (a) is selected from vinyl ester resins or unsaturated polyester resins, and the thermoplastic resin (b) is polybutadiene or a hydrogenated product thereof, polyisoprene or a hydrogenated product thereof, aromatic. Vinyl / conjugated diene block copolymer or hydrogenated product thereof, polystyrene, styrene / vinyl acetate block copolymer, polyvinyl acetate, polymethyl methacrylate, saturated polyester resin, polyether resin, aromatic vinyl / conjugated diene block copolymer The inorganic filler (e) is selected from aluminum hydroxide or titanium oxide.

  That is, in the present invention, firstly, a glass woven fabric and a glass nonwoven fabric impregnated with a thermosetting resin composition are laminated, and the thermosetting resin composition comprises a radical polymerizable resin (a), a heat Containing a plastic resin (b), a radical polymerizable monomer (c), an antioxidant (d) and an inorganic filler (e), wherein the content range of (a) to (c) is (a), (b) and When the total weight of (c) is 100 parts by weight, (a) 10 to 75 parts by weight, (b) 2 to 30 parts by weight, (c) 20 to 60 parts by weight, and the antioxidant (d) The content range is 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of the resins (a) + (b) + (c), and the content range of the inorganic filler (e) is impregnated into the glass woven fabric. In this case, the glass nonwoven fabric is impregnated with 10 to 80 parts by weight with respect to 100 parts by weight of the total resin (a) + (b) + (c) If is set to be by curing the fiber reinforced laminate is from 120 to 300 parts by weight with respect to 100 parts by weight of the total of (a) + (b) + (c).

  Second, the antioxidant (d) is a radical chain inhibitor and / or a peroxide decomposer.

  Third, the inorganic filler (e) is aluminum hydroxide and / or titanium oxide.

  Fourth, the polymer particle (f) having a particle diameter of 0.1 to 5 μm is included.

  Fifth, the CIE 1976 brightness (L *) is 80 or more.

  Sixth, the CIE 1976 brightness (L *) after heat treatment at 170 ° C. for 2 hours is 70 or more.

In the laminate for a printed wiring board on which the first LED of the present invention is mounted , the whiteness of the substrate can be increased, and it is possible to reduce discoloration due to heating of the substrate due to the heat generated by the use of the LED. As a result, high luminance can be maintained.

In the printed wiring board laminate mounting the second LED of the present invention, since the radical chain inhibitor and / or the peroxide decomposing agent are used as the antioxidant (d), the discoloration of the substrate is further reduced. Can do.

In the laminated board for printed wiring boards on which the third LED of the present invention is mounted, since the aluminum hydroxide and / or titanium oxide are used as the inorganic filler (e), the whiteness of the substrate can be further increased.

In the laminated board for printed wiring boards on which the fourth LED of the present invention is mounted , since it contains polymer fine particles (f) having a particle diameter of 0.1 to 5 μm, a sea-island structure using a thermosetting resin and a thermoplastic resin In addition to the formation of, a sea-island structure made of a thermosetting resin and polymer fine particles can be formed, and as a result, the whiteness of the substrate can be further increased.

In the laminated board for printed wiring boards on which the fifth LED of the present invention is mounted , the CIE1976 lightness (L *) is 80 or more. Therefore, when the LED is mounted on the printed wiring board, high luminance can be obtained. .

In the laminate for a printed wiring board on which the sixth LED of the present invention is mounted , the CIE1976 lightness (L *) after heat treatment at 170 ° C. for 2 hours is 70 or more, so the LED is mounted on the printed wiring board. At this time, the luminance is not greatly lowered due to heat generation when the LED is used, and high luminance can be maintained for a long period of time.

  Embodiments of the present invention will be described below.

  The radical polymerizable resin (a) used in the present invention is not particularly limited as long as it is a resin having an ethylenically unsaturated bond, but is produced by adding an ethylenically unsaturated monobasic acid to an epoxy resin. Resins such as vinyl ester resins, dicarboxylic acids necessarily containing an α, β-olefinic unsaturated dicarboxylic acid, and unsaturated polyester resins produced by dehydration condensation reaction of anhydrides and diols are preferred.

  Examples of the thermoplastic resin (b) used in the present invention include thermoplastic resins conventionally used as a low shrinkage agent for unsaturated polyester resins. Examples of such thermoplastic resins include polybutadiene or hydrogenated product thereof, polyisoprene or hydrogenated product thereof, aromatic vinyl / conjugated diene block copolymer or hydrogenated product thereof, polystyrene, and styrene / vinyl acetate block copolymer. There are polymers, polyvinyl acetate, and polymethyl methacrylate, and examples thereof include saturated polyester resins and polyether resins. Of these, aromatic vinyl / conjugated diene block copolymers and saturated polyester resins are preferable, and saturated polyester resins are particularly preferable.

  Examples of the radical polymerizable monomer (c) include unsaturated fatty acids such as acrylic acid and methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, methacrylic acid 2 -Natural carboxylic esters such as hydroxyethyl, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, nitrogen such as (meth) acrylamide, (meth) acrylonitrile Monomer, aromatic vinyl compounds such as styrene, vinyltoluene, divinylbenzene, pt-butylstyrene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanedio Multifunctional (meth) acrylates such as di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate These may be used alone or in combination. Of these, styrene is particularly preferably used.

  The amount of the radical polymerizable resin (a) used is usually 10 to 75 parts by weight, preferably 30 to 67 parts by weight when the total weight of (a), (b) and (c) is 100 parts by weight. is there.

  The amount of the thermoplastic resin (b) used is usually 2 to 30 parts by weight, preferably 2 to 20 parts by weight when the total weight of (a), (b) and (c) is 100 parts by weight. .

  The amount of the radical polymerizable monomer (c) used is usually 20 to 60 parts by weight, preferably 25 to 55 parts by weight when the total weight of (a), (b) and (c) is 100 parts by weight. is there.

  Further, by adding the antioxidant (d), discoloration of the substrate due to heat generated from the LED can be prevented, and high luminance can be maintained over a long period of time.

  Antioxidants (d) used in the present invention include radical chain inhibitors such as BHT, tetrakis (methylene (3,5-di-t-butyl 4-hydroxyhydrocinnamate)) methane, and disteleal. Peroxide decomposing agents such as pentaerythritol diphosphite and trisnonylphenyl phosphite are used alone or in combination. Here, the usage-amount of antioxidant (d) is 0.1-5 weight part with respect to a total of 100 weight part of (a) + (b) + (c). If the addition amount is less than this, the substrate is oxidized and the whiteness is reduced when the substrate is heat-treated. On the other hand, if the amount is too much, the viscosity of the resin composition increases and the productivity may be impaired.

  In order to further increase the whiteness of the substrate, an inorganic filler (e) may be added.

  Examples of the inorganic filler (e) used in the present invention include aluminum hydroxide, titanium oxide and the like, which can be suitably used for increasing the whiteness of the substrate. These inorganic fillers (e) can also be used in combination with glass powder, calcium carbonate, talc, clay, glass balloon, cerium oxide, aluminum silicate, wollastonite, silica, calcium aluminate and the like.

  The average particle diameter of the inorganic filler (e) is preferably 0.2 to 10 μm. When the average particle size is smaller than this, the viscosity of the thermosetting resin becomes too high, impregnation into the glass substrate is lowered, and voids may be generated when the resin is cured. On the other hand, if it is larger than this, convex portions due to the inorganic filler (e) may occur on the surface after the resin is cured.

  Further, in order to improve the dispersibility of the inorganic filler (e), a coupling agent is added to the thermosetting resin, or the inorganic filler (e) that has been surface-treated with the coupling agent in advance is used. Is preferred.

  The particle diameter of the polymer fine particles (f) used in the present invention is usually 0.1 to 5 μm, preferably 0.2 to 2 μm. When the particle diameter is smaller than this, the viscosity of the resin composition increases, which may impair productivity. Conversely, if it is larger than this, the resin composition may not have sufficient toughness.

  The amount of the polymer fine particles (f) used in the present invention is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight in total of (a) + (b) + (c). Part. If it is less than this, the whiteness of the substrate may not increase. On the other hand, when the amount is larger than this, the viscosity of the resin composition becomes high and the productivity may be impaired, and the resin composition itself becomes very expensive.

  In order to cure the resin composition of the present invention, a radical reaction initiator is used. Examples of those used in the present invention include organic peroxides such as methyl ethyl ketone peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide and cumene hydroperoxide.

  As for the usage-amount of a radical reaction initiator, 0.1-3 weight part is preferable with respect to a total of 100 weight part of (a) + (b) + (c).

  The laminate of the present invention is a laminate obtained by laminating three or more fiber reinforcing material layers impregnated with a resin composition containing a radical reaction initiator, and a metal foil, such as copper, on both outer sides as necessary. This laminate can be obtained by placing a foil or the like and then heat-curing the laminate.

A particularly preferred embodiment of the present invention is a composite laminate having a glass woven fabric and a glass nonwoven fabric impregnated as a base material, that is, a laminate for a printed wiring board on which LEDs are mounted . In particular, it comprises a radically polymerizable resin (a), a thermoplastic resin (b), a radically polymerizable monomer (c), an antioxidant (d), and an inorganic filler (e). When the total weight of a), (b) and (c) is 100 parts by weight, (a) 10 to 75 parts by weight, (b) 2 to 30 parts by weight, (c) 20 to 60 parts by weight, The content range of antioxidant (d) is 0.1-5 weight part with respect to a total of 100 weight part of resin (a) + (b) + (c), and inorganic filler (e) is (a) + A glass woven fabric impregnated with a thermosetting resin composition comprising 10 to 80 parts by weight with respect to a total of 100 parts by weight of (b) + (c) is used for the surface layer, (a), (b), When (c), (d) and (e) are included and the content range thereof is 100 parts by weight of the total weight of (a), (b) and (c) (A) 10 to 75 parts by weight, (b) 2 to 30 parts by weight, (c) 20 to 60 parts by weight, and the content range of the antioxidant (d) is resin (a) + (b) + 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of (c), and 120 to 300 parts by weight of inorganic filler (e) with respect to a total of 100 parts by weight of (a) + (b) + (c). A laminate for a printed wiring board on which an LED laminated using a glass nonwoven fabric impregnated with a thermosetting resin composition comprising a part is suitable from the viewpoints of workability, heat resistance, and water resistance.

  In addition to glass woven fabric and glass nonwoven fabric, a woven fabric, nonwoven fabric, or paper base material made of organic synthetic resin fibers may be used depending on the application, or these may be used alone or in combination.

  In addition, clay, talc, wollastonite, silica, magnesium oxide, aluminum silicate, calcium carbonate, or the like may be added to the resin in order to increase the apparent volume of the resin and reduce the cost.

  Hereinafter, the present invention will be specifically described with reference to synthesis examples, formulation examples, examples, comparative examples, and test examples.

Synthesis Example 1 (Synthesis of radical polymerizable resin)
In a 2 liter 4-diameter flask equipped with a stirrer and a thermometer, in the presence of 0.3 g of hydroquinone and 0.3 g of benzyldimethylamine, an epoxy resin (YDB-400, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 400) 800 g 172 g of methacrylic acid was added and reacted at 120 ° C. for 6 hours to obtain a vinyl ester resin having an acid value of 2 mgKOH / g. Thereafter, 457 g of a styrene monomer was added to obtain a vinyl ester resin (A-1) (NV (nonvolatile content) = 68%).

Synthesis Example 2 (Synthesis of radical polymerizable resin)
In a 1-liter 4-diameter flask equipped with a stirrer and a thermometer, 374 g of epoxy resin (YD-128, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 187) in the presence of 0.3 g of hydroquinone and 0.3 g of benzyldimethylamine 172 g of methacrylic acid was added and reacted at 120 ° C. for 6 hours to obtain a vinyl ester resin having an acid value of 2 mgKOH / g. Thereafter, 294 g of a styrene monomer was added to obtain a vinyl ester resin (A-2) (NV = 65%).

Synthesis Example 3 (Synthesis of radical polymerizable resin)
392 g of maleic anhydride, 141 g of propylene glycol and 0.07 g of hydroquinone were charged into a 2 liter 5-diameter flask equipped with a stirrer, a thermometer, a nitrogen gas sealing tube and a partial reflux machine with a thermometer at the top. The mixture was purged with nitrogen and subjected to a dehydration condensation reaction at 200 ° C. for 7 hours to obtain an unsaturated polyester resin having an acid value of 20.4 mgKOH / g. Thereafter, 649 g of a styrene monomer was added to obtain an unsaturated polyester resin (A-3) (NV = 48%).

Synthesis Example 4 (Synthesis of saturated polyester resin)
A 1-liter 5-diameter flask equipped with a stirrer, thermometer, nitrogen gas sealed tube and partial reflux equipped with a thermometer at the top was charged with 438 g of adipic acid, 96 g of propylene glycol, and 117 g of ethylene glycol, and the inside of the container was purged with nitrogen Then, dehydration condensation reaction was performed at 200 ° C. for 8 hours to obtain a saturated polyester resin (B-1) having an acid value of 4.6 mgKOH / g. The number average molecular weight of this resin was 24400.

Synthesis Example 5 (Synthesis of saturated polyester resin)
100 g terephthalic acid, 66 g isophthalic acid, 188 g azelaic acid, 72 g ethylene glycol, neopentyl glycol in a 1 liter 5-diameter flask equipped with a stirrer, thermometer, nitrogen gas sealed tube and partial reflux equipped with a thermometer at the top of the head 96 g was charged, the inside of the container was purged with nitrogen, and subjected to dehydration condensation reaction at 240 ° C. for 9 hours to obtain a saturated polyester resin (B-2) having an acid value of 1 mgKOH / g. The number average molecular weight of this resin was 23900.

Synthesis Example 6 (Synthesis of multilayer structure polymer fine particles)
506 g of deionized water, 2.4 g of 1% sodium dioctylsulfosuccinate aqueous solution and 16.4 g of 1% sodium bicarbonate aqueous solution were charged in a 2 liter polymerization vessel equipped with a reflux condenser, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. did. After raising the temperature, 8 g of ethyl acrylate was added, and after stirring for 10 minutes, 4.1 g of a 2% aqueous sodium persulfate solution was added, and further stirred for 1 hour to obtain a seed latex. Subsequently, after adding 51 g of 2% aqueous sodium persulfate solution at 70 ° C., 663 g of butyl acrylate, 2.4 g of 1,4-butylene glycol diacrylate, 6.7 g of allyl methacrylate, 408 g of 1% aqueous sodium dioctylsulfosuccinate solution, 1% A monomer emulsion forming a first layer comprising 68 g of an aqueous sodium hydrogen carbonate solution was continuously fed over 240 minutes. After completion of the feed, the mixture was further stirred at 70 ° C. for 60 minutes to conduct an aging reaction. Next, 7.2 g of 2% sodium persulfate aqueous solution was added while maintaining the temperature at 70 ° C., and then 101 g of methyl methacrylate, 12 g of ethyl acrylate, 0.6 g of 2-hydroxyethyl methacrylate, 6 g of 1,4-butylene glycol diacrylate A monomer emulsion forming an outermost layer composed of 60 g of a 1% aqueous sodium dioctylsulfosuccinate solution and 12 g of a 1% aqueous sodium hydrogen carbonate solution was continuously fed over 90 minutes. After completion of the feed, the temperature was raised to 80 ° C., and the mixture was further stirred for 60 minutes to conduct an aging reaction. After completion of the ripening reaction, the mixture was filtered through a 300 mesh stainless steel wire mesh to obtain a multilayer polymer latex having a weight average particle size of 0.5 μm. This latex was once frozen at −30 ° C., thawed, dehydrated and washed with a centrifugal dehydrator, and further air-dried at 40 ° C. overnight to obtain multilayer structure polymer fine particles (B-3).

Formulation Examples 1-2
In the weight ratios shown in Table 1, the radical polymerizable resins (A-1) to (A-3) and the styrene monomer obtained in Synthesis Examples 1 to 3 were heated to 80 ° C., and Synthesis Examples 4 to 6 were used. The obtained saturated polyester resins (B-1) to (B-2) and polymer fine particles (B-3) were added and dissolved at 80 ° C. over 3 hours to obtain a resin composition.

Example 1
100 parts by weight of the resin composition of Formulation Example 1, 40 parts by weight of aluminum hydroxide (CL-310, manufactured by Sumitomo Chemical Co., Ltd.), and 80% cumene hydroperoxide (Park Mill H-80 Nippon Oil & Fats) as a radical reaction initiator 1 part by weight and 1 part by weight of antioxidant (Adeka Busta A0-60, manufactured by Asahi Denka Kogyo Co., Ltd.) were added and mixed to obtain a thermosetting resin composition (1), and aluminum hydroxide A mixture obtained by adding 140 parts by weight and 1 part by weight of 80% cumene hadperoxide was used as a thermosetting resin composition (2). Glass woven fabric for laminated plates (WE-18K-BS, manufactured by Nittobo Co., Ltd.) impregnated with thermosetting resin composition (1), one layer, glass nonwoven fabric (Ep-4060, 60 g / m2, Japan) Vilain Co., Ltd.) 3 layers impregnated with the thermosetting resin composition (2), and 1 layer of glass woven fabric impregnated with the thermosetting resin composition (1) are sequentially laminated, A copper foil having a thickness of 18 μm was stacked on both sides, and cured by heating and pressing at 100 ° C. for 30 minutes and 175 ° C. for 30 minutes to obtain a laminate having a length and width of 150 mm and a thickness of 1.6 mm.

Example 2
100 parts by weight of the resin composition of Formulation Example 2, 40 parts by weight of aluminum hydroxide (CL-310, manufactured by Sumitomo Chemical Co., Ltd.), and 80% cumene hydroperoxide (Park Mill H-80 Nippon Oil & Fats) as a radical reaction initiator 1 part by weight and 1 part by weight of an antioxidant (Adeka Busta A0-60, manufactured by Asahi Denka Kogyo Co., Ltd.) were added and mixed to obtain a thermosetting resin composition (3), and 140 wt. Part, 80% cumene hadperoxide 1 part by weight was added and mixed to obtain a thermosetting resin composition (4). Glass woven fabric for laminate (WE-18K-BS, manufactured by Nittobo Co., Ltd.) impregnated with thermosetting resin composition (3), one layer, glass nonwoven fabric (Ep-4060, 60 g / m2, Japan) Vilain Co., Ltd.) 3 layers impregnated with the thermosetting resin composition (4), and 1 layer of glass woven fabric impregnated with the thermosetting resin composition (3) are sequentially laminated, A copper foil having a thickness of 18 μm was stacked on both sides, and cured by heating and pressing at 100 ° C. for 30 minutes and 175 ° C. for 30 minutes to obtain a laminate having a length and width of 150 mm and a thickness of 1.6 mm.

Example 3
100 parts by weight of the resin composition of Formulation Example 1, 30 parts by weight of titanium oxide (anatase type, particle size 0.4 μm), and 80% cumene hydroperoxide as a radical reaction initiator (Park Mill H-80 Nippon Oil & Fat Co., Ltd.) 1 part by weight and 1 part by weight of an antioxidant (Adeka Busta A0-60, manufactured by Asahi Denka Kogyo Co., Ltd.) were added and mixed to obtain a thermosetting resin composition (5), and 140 parts by weight of aluminum hydroxide Then, 1 part by weight of 80% cumene hadperoxide was added and mixed to obtain a thermosetting resin composition (6). Glass woven fabric for laminate (WE-18K-BS, manufactured by Nittobo Co., Ltd.) impregnated with thermosetting resin composition (5), one layer, glass nonwoven fabric (Ep-4060, 60 g / m2, Japan) Vilain Co., Ltd.) 3 layers impregnated with the thermosetting resin composition (6), and 1 layer of glass woven fabric impregnated with the thermosetting resin composition (5) are sequentially laminated, A copper foil having a thickness of 18 μm was stacked on both sides, and heated and pressurized at 100 ° C. for 30 minutes and 175 ° C. for 30 minutes to obtain a laminate having a length and width of 150 mm and a thickness of 1.6 mm.

Example 4
100 parts by weight of the resin composition of Formulation Example 2, 30 parts by weight of titanium oxide (anatase type, particle size 0.4 μm), and 80% cumene hydroperoxide (Park Mill H-80 Nippon Oil & Fats Co., Ltd.) as a radical reaction initiator 1 part by weight) and 1 part by weight of an antioxidant (Adeka Busta A0-60, manufactured by Asahi Denka Kogyo Co., Ltd.) were added and mixed to obtain a thermosetting resin composition (7), and 140 parts by weight of aluminum hydroxide Then, 1 part by weight of 80% cumene hadperoxide was added and mixed to obtain a thermosetting resin composition (8). Glass woven fabric for laminate (WE-18K-BS, manufactured by Nittobo Co., Ltd.) impregnated with thermosetting resin composition (7), one layer, glass nonwoven fabric (Ep-4060, 60 g / m2, Japan) Vilain Co., Ltd.) 3 layers impregnated with thermosetting resin composition (8), and 1 layer of glass woven fabric impregnated with thermosetting resin composition (7), respectively, A copper foil having a thickness of 18 μm was stacked on both sides, and cured by heating and pressing at 100 ° C. for 30 minutes and 175 ° C. for 30 minutes to obtain a laminate having a length and width of 150 mm and a thickness of 1.6 mm.

Comparative Example 1
In Example 1, a laminate was obtained in the same manner except that no antioxidant was added.

Comparative Example 2
In Example 2, a laminate was obtained in the same manner except that no antioxidant was added.

Comparative Example 3
In Example 3, a laminate was obtained in the same manner except that no antioxidant was added.

Comparative Example 4
In Example 4, a laminate was obtained in the same manner except that no antioxidant was added.

Test Example Whiteness Measurement After etching the obtained laminate, using a color difference meter (model: TC-8600A, manufactured by Tokyo Denshoku Co., Ltd.), after etching (initial) and after treatment at 170 ° C. for 2 hours CIE 1976 brightness (L *) was measured.

  Here, the CIE 1976 brightness (L *) is an amount that is approximately correlated with the brightness, calculated in the uniform color space recommended by the CIE (International Lighting Commission) in 1976.

  The measurement results are shown in Table 2.

  As is clear from Table 2, in the laminates of Examples 1 to 4 of the present invention, a composite laminate having high whiteness is obtained by curing the thermosetting resin and the thermoplastic resin so as to form a sea-island structure. The board could be obtained.

  Moreover, whiteness can be made higher by using polymer fine particles or titanium oxide.

Moreover, the fall of the whiteness by heating discoloration can be reduced by adding antioxidant.

Claims (6)

A glass woven fabric and a glass nonwoven fabric impregnated with a thermosetting resin composition are laminated, and the thermosetting resin composition comprises a radical polymerizable resin (a), a thermoplastic resin (b), and a radical polymerizable monomer. (C), an antioxidant (d), and an inorganic filler (e), wherein the radical polymerizable resin (a) is selected from a vinyl ester resin or an unsaturated polyester resin, and a thermoplastic resin (b ) Is polybutadiene or hydrogenated product thereof, polyisoprene or hydrogenated product thereof, aromatic vinyl / conjugated diene block copolymer or hydrogenated product thereof, polystyrene, styrene / vinyl acetate block copolymer, polyvinyl acetate, polymethyl The inorganic filler (e) is selected from methacrylate, saturated polyester resin, and polyether resin. Is selected from a beam or titanium oxide, in the case where (a) containing a range of ~ (c) is set to (a), the total weight 100 parts by weight of (b) and (c), (a) 10 -75 parts by weight, (b) 2-30 parts by weight, (c) 20-60 parts by weight, and the content range of the antioxidant (d) is a total of 100 weights of (a) + (b) + (c) (D) 0.1 to 5 parts by weight, and when the content range of the inorganic filler (e) is impregnated into the glass woven fabric, a total of 100 weights of (a) + (b) + (c) When impregnating 10 to 80 parts by weight with glass nonwoven fabric, the fiber reinforced laminate that is 120 to 300 parts by weight is cured with respect to a total of 100 parts by weight of (a) + (b) + (c). A printed wiring board substrate on which an LED is mounted .
The laminate for a printed wiring board on which the LED according to claim 1 is mounted, wherein the antioxidant (d) is a radical chain inhibitor and / or a peroxide decomposer. The laminated board for a printed wiring board on which the LED according to any one of claims 1 and 2, wherein the inorganic filler (e) is aluminum hydroxide and / or titanium oxide. The laminated board for printed wiring boards which mounts LED in any one of Claims 1-3 characterized by including the polymer microparticles | fine-particles (f) with a particle diameter of 0.1-5 micrometers. CIE1976 lightness (L *) is a LED according to any one of claims 1 to 4, both particle size If it is 80 or higher, characterized in that it comprises a polymer fine particle (f) of 0.1~5μm Laminated board for printed wiring board to be mounted . 6. CIE1976 lightness (L *) after heat treatment at 170 ° C. for 2 hours is 70 or more, and comprises polymer fine particles (f) having a particle diameter of 0.1 to 5 μm. A laminate for a printed wiring board on which the LED according to any one of the above is mounted .