JPS5894448A - Molding material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molding material having significantly improved flexural modulus and impact strength by impregnating a composite reinforcement with a resin.

Conventionally, fibrous reinforcing materials are made into a mat or cloth shape, impregnated with thermosetting resin by hand lay-up, preform matted metal die, resin injection method, etc., and composite molded to obtain reinforced plastics. Thermoplastic resin sheet molding method, etc.
A method for obtaining reinforced plastics by composite molding of Tffi resin is known. In addition, in order to impart properties such as direct elastic modulus, heat resistance, electrical insulation, chemical resistance, isotropy, and barrier resistance, we use thermosetting and heat-resistant scaly inorganic reinforcing fillers such as mica flakes. A method is also known in which reinforced plastics are obtained by homogeneously mixing them into a plastic resin by melt-kneading or the like, and then molding the mixture. A method is also known in which a fibrous reinforcing material and a scaly IIA reinforcing filler are simultaneously mixed to take advantage of their advantages, or a resin mixed with the latter is impregnated into the former in the form of a mat or cross. However, in a combination system of fibrous reinforcing material and scale-like inorganic reinforcing filler, that is, a homogeneous mixture of double-sided reinforcing material, it is difficult to achieve a sufficient reinforcing effect with a well-balanced balance between elastic modulus, strength, and impact resistance. In addition, when the scale-like inorganic reinforcing filler is mixed with the resin, the resin viscosity increases, causing low flLm properties, resulting in molding defects such as poor impregnation, poor defoaming, and poor filling, and insufficient interlaminar strength. Because of the drawbacks, the range of use of the flaky reinforcing filler was limited, and its properties could not be fully utilized.The present inventors have conducted extensive studies to eliminate the above drawbacks. As a result, the scale-like inorganic reinforcing filler, which is difficult to disperse in resin, is sandwiched between fibrous reinforcing materials to form a composite reinforcing material, and this is impregnated with resin, thereby eliminating problems when mixing the filler into resin. The present invention was completed based on the new discovery that a molded product with excellent bending elastic modulus and impact resistance can be obtained based on the mechanical properties of the reinforcing material and the filler.

That is, the present invention provides a composite reinforcing material comprising (a) two or more fibrous reinforcing material layers and (b) one or more scaly inorganic reinforcing filler layers sandwiched between the fine reinforcing material layers. It is a molding material made by impregnating resin with resin.

The scaly inorganic reinforcing fillers used in the present invention include natural or synthetic mica such as phlogopite, muscovite, and fluorinated mica, and those conventionally used as scaly inorganic reinforcing fillers such as talc and glass flakes. Among them, mica is preferred. These fillers may be used alone or in combination of two or more shelves. In order to impart affinity with the resin, known surface treatments such as silane treatment and bola treatment are performed as necessary. The shape of the filler is preferably one in which the M amount average flake diameter is 2Uμ or more and the Chonghui average aspect ratio is 10 or more from the viewpoint of reinforcing effect, and from the viewpoint of the relationship with the fibrous reinforcing material, the weight average The flake diameter is preferably 100μ or more. Although such flakes may be sprinkled on the edge of the reinforcing material I to be described later to form a layer, it is preferable that they are joined with a binder to form a filler layer.

Since the filler layer only needs to be formed to the extent that it is easy to handle, the amount of binder added may be as small as about 1 to 10% (based on the filler). As the binder, a single resin or a mixture of two or more resins such as saturated/unsaturated polyester resin, vinyl acetate resin, ethylene vinyl acetate resin, Ebochishi resin, urethane resin, etc., which are commonly used in the field of resin molding, is used. Among these, unsaturated polyester resins are common. These powders are used in the form of an emulsion and the powder G is used in the form of an emulsion to bind the filler.

Various inorganic and organic fibers such as glass fiber, polyvinyl alcohol fiber, carbon fiber, alumina fiber, polyester fiber, cellulose fiber, and nylon fiber are effective as the fibrous reinforcing material used in the present invention. However, glass fibers and bobbinyl alcohol fibers are preferred. These fibers can be used alone or in combination of two or more fibers. Furthermore, the delicate reinforcing material can be used after being subjected to known surface treatments such as silane treatment and borane treatment in order to have affinity with the resin used.

These fibrous reinforcement materials include short fiber mats (chopped strand mats, etc. in the case of glass fibers), long fiber mats (
In the case of glass fibers, a layer is formed in the form of a non-woven fabric, a fibrillated sheet (such as a swirl mat), or a skin is formed in the form of a satin-woven fabric, a plain-woven fabric, or a knitted fabric. Commercially available mats or cloths for resin reinforcement can also be used as they are.

In the present invention, a filler layer is sandwiched between the above-mentioned two reinforcing material layers to form a composite reinforcing material, and such a composite reinforcing material is formed as follows. A mat or cloth of fibrous reinforcing material is prepared in advance by a known method, a piece of inorganic reinforcing filler is spread on it to form a layer, and then a mat or cloth of fibrous reinforcing material is further formed on top of the mat or cloth of fibrous reinforcing material. It can be formed by placing a cloth, or by sprinkling a scale-like inorganic reinforcing filler containing a binder on a pre-prepared commercially available mat or cloth, and then laminating a commercially available mat or cloth on top of it, and after crimping. There are methods of integrating the reinforcing material layer and the filling material layer by cooling and melting the binder on the surface of the filling material, but the latter method is particularly preferred in terms of handling of the composite reinforcing material. The forming method is not limited to the above-mentioned method as long as the scale-like inorganic reinforcing filler layer is sandwiched between fibrous reinforcing material layers.

In the present invention, there is no particular restriction on the ratio of the filler layer to the reinforcing material layer, and depending on the application, for example, if rigidity is required, the weight of the filler layer may be increased, and if strength is required, the weight of the filler layer may be increased. This is done by increasing *m of the reinforcing material layer. Usually, the weight of the filler layer and the reinforcing material/liter (one side) is each selected in the range of 50-600 g 7 m2.

The molding material of the present invention is formed by impregnating the above-mentioned composite reinforcing material with a resin. In the present invention, applicable resins include saturated/unsaturated polyester resins, vinyl ester resins, epoxy resins, and phenolic resins. , various thermosetting resins such as polyurethane resins, and various thermoplastic resins such as polyvinyl chloride, polyolefin, nylon, and polyester resins. Among them, unsaturated polyester 4
ii fat is usually used. The amount of impregnated Iillwj is selected depending on the application, but usually the ratio of filler + reinforcing material to wood is in the range of 1:9 to 8:2 by weight. Incidentally, a coupling agent such as a silane coupling agent or a titanate coupling agent and a modifier may be appropriately added to these resins in order to give them affinity with the above-mentioned composite reinforcing material. Furthermore, if necessary, inorganic powders such as calcium carbonate, clay, kaolin, aluminum hydroxide, calcium silicate, silica sand powder, fly ash powder, slag powder, gypsum, glass peas, and other i:Ir flexibility may be added to the resin. A low shrinkage agent, a coloring agent, a flame retardant, a curing agent, an internal mold release agent, etc. may be added.

In the present invention, the molding methods for impregnating the composite reinforcing material with resin include hand lay-up method, press molding method, resin injection method, etc. for thermosetting resin, and extrusion molding method, press molding method, and resin injection method for thermoplastic resin. Examples include calendar molding method. By this method, it can be impregnated with resin and simultaneously molded into a desired molded product, or it can be hot press molded as an intermediate molded product such as 8MG or prepreg mat, or it can be formed into other sheet shapes. It is also possible to form a molded article by laminating materials.

As described above, the present invention is characterized by using a composite reinforcing material in which a filler layer is sandwiched between reinforcing material layers, and the use of such a composite reinforcing material exhibits the following effects.

When kneading reinforcing materials and fillers together into a resin, or when impregnating a reinforcing material layer with resin mixed with fillers, the viscosity of the resin increases when the fillers are mixed, so the amount of filler used is (In the case of unsaturated polyester resin, the filler concentration in l7jIA fat is limited to about 18%.) and the scale-like filler is not oriented in a layered manner. The reinforcing effect could not be fully utilized. On the other hand, in the composite reinforcing material of the present invention, since the resin permeates into the filler layer, the concentration of the filler in the resin decreases (in the case of unsaturated polyester, the concentration of the filler in the resin increases by 50%). %), and since the scaly filler is easily oriented within the layer, the properties of the filler are exhibited. Furthermore, in the present invention, a flake-like filler layer with an unstable shape is sandwiched between stable fibrous reinforcing material layers, so it is difficult to obtain a stable composite reinforcing material that is easy to handle. can. In addition, it is possible to exhibit both the mechanical properties of the fibrous reinforcing material and the properties of the scale-like filler.

As described above, in the present invention, the reinforcing material layer - the filler layer -
Although a composite reinforcing material having a 3) f1 structure of the reinforcing material layer is basically used, it is possible to laminate further layers thereon, and the present invention is not limited to a five-layered structure. For example, a filler layer is further placed on a 3-layer structure to create a 4@ structure (further, a 6-layer structure with a reinforcing material layer and a filler layer, etc.) (the filler layer on the surface improves surface smoothness and design. , barrier resistance, etc.), and a 5-layer structure with a filler layer and a reinforcing material layer added to the 5-layer structure (and a 7-layer structure with a filler layer and a reinforcing material layer, etc.) ), an embodiment in which the above-mentioned five-layer structure is laminated to a thickness of 2M or more, and an embodiment in which both sides of a six-layer structure are each further provided with a reinforcing material layer or a filler layer.

The molding material of the present invention can be used in the following applications: 16. The molding material of the present invention, in which the composite reinforcing material layer is impregnated with a thermosetting resin, can be used for structural parts, small ships, bathtubs, bath units,
It is used in tanks, automobile-related parts, electrical parts that take advantage of performance such as IF# characteristics and insulation, communication equipment-related parts, marine-related parts, etc.
The molding material impregnated with J-plastic resin can be used as a flat plate or shaped by methods such as press molding and stamping molding to produce automobile-related parts, tanks, electrical parts that take advantage of performance such as smoothness and insulation, and hooks. , used for office equipment, good luck products, and communication equipment related parts. In addition, most applications where reinforcing material layers are currently used include
However, it is not limited to the above uses.

The molding material of the present invention will be specifically explained below using Examples and Comparative Examples.

Example 1 Glass chopped strand mat CM-300 (fiber diameter 13μ, fiber length approximately 5cm, weight 500g/m', average grain size 260μ, aspect ratio 70 Sugilite on top of Asahi fiberglass!i!) Mica (MfLI!l&ri2
25 g/m' and unsaturated polyester IMHJI [Pufflac 8 people - 225 (Dainippon Ink Chemical @%)
37 g 7 m" of the mixture was laminated, and the glass chopped strand mat CM-600 was further laminated on top of the glass chopped strand mat CM-600, and the mixture was pressed at a temperature of 140°C and a pressure of 1 kg/c+u2, and then cooled to form approximately 850 g 7 m2 of glass. A composite reinforcing material consisting of chopped strands-mica was manufactured.

The composite reinforcing material was impregnated with unsaturated polyester resin (Yubica 2055F (Japan Upica*)) mixed with 1% Vermec N (manufactured by Nippon Oil & Fats Co., Ltd.) as a catalyst, and in a semi-cured state at room temperature. 6- with the same composition in the same manner
Laminated to a thickness of 4.7mm with glass-mica content of 55% electrical capacity.
An unsaturated polyester resin laminate containing (mica concentration in resin +2.8'Mii%) was produced. The results of measuring the performance of the laminate are shown in Table 1. The bending performance was measured according to Mu8TM-D-79D. Also,
Izot impact strength was measured with a notch according to A8TM-D-256.

Example 2 225 g 7 m2 of Suzolite mica with an average particle size of 40 μm and an aspect ratio of 50 and 10 g/m of unsaturated polyester resin (Panolac B-225) were used.
An unsaturated polyester resin laminate having the same composition and the same method as in Example 1 and having a thickness of 4.7 threshold and containing about 55 g of glass-mica was manufactured. Table 1 shows the performance measurement results of this laminate.

Example 5 - A glass chopped strand mat of 350 g/in'' with a diameter of 15 μm and a fiber length of about 5 am was produced, and on top of the mat was 125 g/m” of Sugilite mica with an average particle size of 1400 μm and an aspect ratio of 90. and unsaturated polyester-fd
Jll (Panorak B M-225) 5 g/m' mixture was laminated, and the above-mentioned 550 g/m' glass chopped strand mat was laminated thereon, and the temperature was 140°.
Crimp at C1 pressure IQ/am' and cool to about 83
A composite reinforcement consisting of 0 g/m'' glass chopped strands-mica was produced.

Unsaturated polyester tree II mixed with 1% by weight of Permec N as a catalyst and 5% by weight of silane coupling agent Mu-1870! The composite reinforcing material was impregnated with V (Yupica 2055P), and in a semi-cured state at room temperature, 511JJ of the same composition was sequentially layered in the same manner, and after curing at room temperature for 1 day and night, it was cured at 80 C. After curing, the thickness is approximately 4.9 hours.
An unsaturated polyester resin laminate having a glass-mica content of 55% by weight was produced at m. Table 1 shows the performance measurement results.

Example 4 2S Og 7m with fiber diameter 15μ and fiber length approximately 5am
A glass chopped strand mat of `` was produced, and on top of the mat was added 560 g/m2 of Sugilite mica with an average particle size of 260 μm and an aspect ratio of 70, and 10 g/m2 of unsaturated polyester tree TII & (Panorac B M-223). 230g of 7m”
Laminated glass chopped strand mats with temperature 1
A composite reinforcing material made of glass-mica of approximately 850 g and 7 m'' was produced by pressing at 40°C and a pressure of I Kg/am'' and cooling. The composite reinforcing material was laminated in five layers using the same resin and the same method as in Example 1 to a thickness of 4.7 mm, and the glass-mica content was approximately 5-51% by weight (the mica concentration in the resin was 19.5% by weight). ) was produced. Table 1 shows the performance measurement results.

Example 5 Same composition and same method as Example 1.
．． A 2 m unsaturated d-lyester resin laminate containing about 55% by weight of glass mica was produced. Table 1 shows the performance measurement results.

Comparative Example 1 Glass chopped strand mat CM-455rm (
Asahi Fiberglass) as a catalyst /< - MEC N
Unsaturated polyester wood W (Yupica 2) mixed with 1% by weight
55 layers of glass fiber JI1 with a thickness of about 4.5 strokes were laminated in 5 layers using the Enichi method as in Example 5, except for impregnating it with ossr).
% unsaturated polyester laminates were produced. Table 1 shows the performance measurement results.

Comparative Example 2 15% by weight of Sugilite mica with an average particle size of 260 μm and an aspect ratio of 70, 9% by weight of Permec N O and an unsaturated polyester resin (Yubica 2055F) 86.1
After thoroughly mixing the weight percentages and defoaming, the composition was impregnated into a glass chopped strand mat CM-600 (manufactured by Asahi Fiberglass), and in a semi-cured state with am. CM-boo
Repeated impregnation and semi-curing, laminated 3 layers, cured at room temperature for 1 day and night, then cured at 80"C for 4 hours to a thickness of about 4.5".
An unsaturated polyester resin laminate of 8 mm and containing 55% by weight of glass-mica was produced. Table 1 shows the performance measurement results. When mica is mixed with resin,! Since the MpIiI viscosity increased, it became difficult to impregnate the resin into the mat, and impregnation also took time, resulting in poor workability.

Comparative Example 5 Sugilite mica 19.5, 1ij 1% with an average particle size of 260μ and an aspect ratio of 70, Permec N 088g% and unsaturated polyester tree jii (Yubica 2055
F) After thoroughly mixing 79.9% by weight and defoaming, the composition was impregnated into Glass Chopped Strand Mat CM-455F in a semi-cured state at room temperature. Repeated impregnation and semi-curing with 455F, laminated 3 layers, cured at room temperature day and night, and then cured at 80'O for 4 hours to a thickness of about 4.8mm.
Unsaturated polyester containing 351j1% of glass-mica! Manufactured M shield horizontal pigeon board. Table 1 shows the performance measurement results. In this case, the mica concentration in the resin was 19.5%.
As a result, the viscosity of the resin increased and the impregnation became steeper, making the impregnation work more laborious. Furthermore, since a product uniformly impregnated with resin could not be obtained, the physical properties of the horizontal laminate were also poor.

Comparative Example 4 Glass chopped strand mat CM-600,60
Unsaturated polyester tree containing 0g/m' by 81% of Vermec 2055F) 1000g 7
m” and formed a semi-hardened layer at room temperature, on which Sugilite Mica 2 with an average particle size of 260μ and an aspect ratio of 7o is applied.
Composition of unsaturated polyester resin (Yupica 2055r) containing 0.5m filtration% and 18% by weight of Permec N0 @ 1650
After defoaming, laminated the 7m” g.g.
4. Sequentially glass chopped strand layer, mica layer, glass chopped strand layer and 51! ll laminated, cured at room temperature for one day and night, and then post-cured at 80@C for 4 hours to produce an unsaturated Bossester wood laminate having a thickness of about 4.8 mm+ and containing 55% by weight of glass-mica. .

Performance measurement results are shown in Figure 1.

Example 6 The same composition as in Example 1 was used, except that talc (talcan powder PNP) with an average particle size of 24 μm and an aspect ratio of 15 was used instead of Sugilite mica, and the same method was used to produce a glass-talc material with a thickness of 4.7 mm and a glass-talc diameter of 55 μm. An unsaturated polyester resin laminate containing %.

Table 1 shows the performance measurement results.

Example 7 A glass chopped strand mat of 2S Og 7m" was produced, and on the mat 500g of Sugilite mica with an average particle size of 260μ and an aspect ratio of 70/Gato unsaturated polyester tree JII (Banolac B 225)
15 g/m' of the mixture was laminated, and the 250 g/m' of glass chopped strand mat was further laminated thereon, and the mixture was heated to 140° C. and 1 g/amp at a pressure of 1.
The material was crimped and cooled to produce a composite reinforcement material with a weight of about 970 g/m'. Unsaturated polyester resin (Yubica 2035P) mixed with Permec N111Ii weight% as a tactile agent
The composite reinforcing material was impregnated in a semi-cured state at room temperature, and 5 layers of the same composition were sequentially laminated in the same manner, followed by curing at room temperature day and night, and then post-curing at 80"O for 4 hours. ,
Unsaturated polyester with a thickness of 4.5m and containing approximately 41% by weight of crow-mica (mica concentration in the resin: 26.5%)! M-wood laminate was manufactured. Table 1 shows the performance measurement results.

Example 8 F57. 'yoy, WE-18K-104BZ-2
(Nitto Junsen, fiber diameter 13 μ, weight 207 g/m”) and Sujirite mica 200 g/m’ with average particle size 260 μ and aspect ratio 70 and ethylene vinyl acetate V j
L+Jean 0N-600 (manufactured by Kuraray) 10 g/m
'Layer the mixture of ', and then add glass cloth WE
-18 was laminated with 104BZ-2 and the emulsion water was evaporated at 11°0C to produce a composite reinforcement consisting of about 620 g/m' of glass cloth-mica. Diaminodiphenyl sulfone 2ammm.

Monoethylamine trifluoride monoethylamine acetate salt (trade name BFL-
400 manufactured by Hashimoto Kasei Kogyo Co., Ltd.) was dissolved in the solution, and 1 part by weight of the epoxy resin Epicoat 828 (Shell Chemical Exhibition) was dissolved in the solution.
Epoxy hardener solution 4 to which 100 parts JIi was added and mixed uniformly? The composite reinforcement material was impregnated with 100 g/m'' of methyl ethyl ketone at a temperature of 90°C and dried for 8 minutes at a temperature of 160°C (7) rM to obtain a prepreg cloth of approximately 895 g/m'. 16011C15Kg/Cm immediately after laminating 4 layers of the prepreg cloth and heating at 160°C for 20 minutes.
After heat pressing at a pressure of 2 for 50 minutes, t a (1@0
After 2 hours of curing, an epoxy horizontal laminate having a thickness of 1.15 mm and containing 70% by weight of glass-mica was obtained. Table 1 shows the performance measurement results. The molded product performance in Table 1 shows numerical values in the longitudinal direction.

Comparative Example 5 tf7. ')OSWE-181-104BZ-2 500g 7mff prepreg cloth was manufactured and C
, C1) Example 7 with 12N1 horizontal layers of prepreg cloth
Heat press and post-cure in the same manner as above to a thickness of 1 or 8.
An epoxy laminate containing approximately 70% by weight of crow-mica was prepared with mrn. Table 1 shows the performance measurement results. The performance of the molded product in Clothing 1 is shown in the vertical direction.

Patent Deku University Kurashi Co., Ltd. Representative Patent Attorney Ken Honda

Claims (1)

[Claims] (1) (a) two or more fibrous reinforcing material layers; and (b) one or more scaly inorganic reinforcing filler layers sandwiched between the fibrous reinforcing material layers. A molding material made of a composite reinforcing material impregnated with resin. (2) The molding material according to claim 1, wherein the scaly inorganic reinforcing filler is mica flakes. (3) The molding material according to claim 2, wherein the mica flakes have a weight average flake diameter of 20 μ or more and a weight aspect ratio of 10 or more. (4) The molding material according to claim 1, wherein the filler layer is a layer formed by bonding the filler with a binder. (5) The molding material according to claim 4, wherein the binder is used in an amount of 1 to 10% by weight based on the filler. (6) The molding material according to claim 4, wherein the binder is an unsaturated polyester resin. (7) The molding material according to claim 1, wherein the fibrous reinforcing material is glass fiber. (8) The molding material according to claim 1, wherein the fibrous reinforcing material is a polyvinyl alcohol synthetic fiber. (9) The molding material according to claim 1, wherein the reinforcing material layer is a mat or a woven fabric. 00) The molding material according to claim 1, wherein the filler layer and the reinforcing material layer each have a weight in the range of 50 to 600 g/m'. (11) The M filling material layer and the reinforcing material layer are crimped together,
The molding material according to claim 1, wherein the binder on the surface of the filler layer is melted and integrated. The molding material according to claim 1, wherein the resin is a thermosetting resin or a thermoplastic resin. 13. The molding material according to claim 12, wherein the thermosetting resin is an unsaturated polyester resin. Mochi) The ratio of the filler + the reinforcing material to the resin is 1:9 ~
8:2 molding material according to claim 1. (to) The molding material according to claim 1, wherein the reinforcing material layer is two layers and the filler layer is one layer. (16) The molding according to claim 1, wherein the reinforcing material layer and the filler layer are each two layers, and one of the filler layers is sandwiched between the two reinforcing material layers. material. 07) The molding material according to claim 1, wherein the reinforcing material layer has five layers, and two filler layers are sandwiched between each of the reinforcing material layers. . (To) A composite reinforcing material comprising (a) two or more fibrous reinforcing material layers and to) one or more scale-like inorganic reinforcing filler layers sandwiched between the fibrous reinforcing material layers.