JPS6143661A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A composition useful as a structural material such as building materials, ships, etc., providing a lightweight cured material having high strength, obtained by using a polyolefin fibrous material having high strength as a reinforcing material for a thermosetting resin. CONSTITUTION:(A) A polyolefin fibrous material having high strength, preferably highly crystalline polyethylene, is mixed with paraffin wax, extruded by a screw extruder, immersed in n-hexane, etc. to remove the paraffin wax, oriented and drawn, to give a polyethylene fibrous material having >=0.5GPa tensile strength at break point at normal temperature and >=15GPa modulus in tension, which is preferably subjected to plasma treatment, is impregnated with (B) a thermosetting resin, preferably epoxy resin varnish, to give prepreg or laminate. An impregnated amount of the component B is 20-70wt%, preferably 30-50wt% in a composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermosetting resin composition. More specifically, the present invention relates to a thermosetting resin composition that can provide a lightweight and high-strength cured product.

[Conventional technology]

Thermosetting resins such as epoxy tree manure can be used for example with metal fibers,
It is well known that glass fibers are used for reinforcement, but recently carbon jam has been used as a reinforcing material that has both lightweight and reinforcing properties. However, further weight reduction of such reinforced resin materials is a strong demand of the times in connection with the problem of energy conservation.

[Problem that the invention seeks to solve]

Based on this request, the present inventors conducted various studies in search of a reinforced resin material that was lighter in weight while still maintaining sufficient strength as originally required.As a result, the present inventors developed a high-strength polyolefin fiber that has a specific gravity even lower than that of carbon fiber. It has been found that this problem can be effectively solved by using a thermosetting resin as a reinforcing material.

[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a thermosetting resin composition capable of providing a lightweight and high-strength cured product, and this thermosetting resin composition and high strength polyolefin fibrous material.

Examples of thermosetting resins include epoxy resins, phenolic resins, polyimide resins, unsaturated polyester resins, and alkyds! Polymer resins, urea resins, melamine resins, etc. are used, and these may be in the form of oligomers or prepolymers.

Preferred among these thermosetting resins are epoxy resins, such as bisphenol A type epoxy resin, bisphenol R type epoxy resin, phenol novolac type epoxy side L cresol novolac type epoxy resin,
Alicyclic epoxy resins, heterocyclic epoxy resins such as triglycidyl isocyanate and hydantoin epoxy,
°Hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin such as propisine glycol diglycidyl ether and pentaerythritol polyglycidyl ether, epoxy resin obtained by reaction of aliphatic or aromatic carboxylic acid with epichlorohydrin, spirocycle-containing epoxy resin Epoxy resin, 0-allylphenol novolac compound, glycidyl ether type epoxy resin which is a reaction product with tobichlorohydrin, diallylbisphenol compound having an allyl group at the 0-position relative to each hydroxyl group of bisphenol A, and epichlorohydrin. Glycidyl ether type epoxy resin, which is a reaction product of , is used. These epoxy resins have an epoxy equivalent of about 70 to 3300, preferably about 100 to 1000,
The softening point (according to the Durand method) is about 60 to 150°C, preferably about 65 to 95°C, and the viscosity (at 25°C) is about 10 to 150°C.
30000 cps, preferably about 1000-150
00 opm is generally used.

Of course, if epoxy 4[ is used, curing agents known for it, such as boron trifluoride amine complexes, tertiary amines, quaternary ammonium salts, borate compounds, imidazole compounds, Metal salt compounds, amide compounds, urea compounds, melamine compounds, incyanate compounds, cyanate compounds, phenolic compounds, aromatic or aliphatic amine compounds, acid anhydrides, boron
]Amine compounds etc. are generally used in combination.

Other thermosetting resins include phenolic resins obtained by the reaction of phenols and aliphatic aldehydes; and a novolak tree m obtained by a condensation reaction. The former company, general IC, is in liquid or paste form, so it is suitable for curing after blending other ingredients, and for the latter, it is important to sufficiently control the reaction and keep it in a prepolymer state. . These phenolic resin-like, viscosity (2
5°C) is about 100 to 10,000 cps, preferably about 200 to 5,000 cps, and the softening point is about 50 to 5,000 cps.
A temperature of 150°C, preferably about 70-110°C is generally used.

As curing agents for novolac type pheno-1-resins, commonly used hexamine, paraformaldehyde, resol type phenol resins, etc. are used.

Polyimide resin as a thermosetting resin has the general formula, R-
(in,)Y [Here, R is a divalent organic group, and n is a certain enemy of 2 or more] and the general formula A +1 ("0ゝB)", where A is At least \00/'
m is also an organic group having 2 carbon atoms, and m is 2 to 4] or a pre-reacted product thereof.

Polyamine companies, such as hexamethylene diamine,
p-phenylenediamine, +,4-diaminodiphenylmethane, 4. <-diaminodiphenyl ether, 4° diamino diphenyl ketone, 4° diamino diphenyl sulfone, xylylene diamine, and the like.

In addition, unsaturated bismaleimides include, for example, H, M'
-722lane bismaleimide, M,H'-hexamethylene bismaleimide, N,N'-methylene-jip-
Phenylene bismaleimide, NIN'-oxy-')
-p-phenylene bismaleimide, WIN' 41
4'-benzophenone bismaleimide, N, N'-p-
diphenylsulfonemaleimide, N,N'-(3,3
'-dimethyl)-methylene di-p-722lene bismaleimide, N, N'-4,4'-dimethylhexylmethane bismaleimide, N, N'-m (mata p)-xylylene bismaleimide, N , N'-(3,3'-diethyl)methylene-di-p-7 22lene bismaleimide, N,
li' m-toluylene cymaleimide, etc., and these unsaturated bismaleimides can be reduced to about 60ffiffi% with monomaleimide compounds such as N-allylmaleimide, N-propylmaleimide, N-hexylmaleimide, and N-phenylmaleimide. It can also be used instead.

The polyimide resin prepared from each of these components includes the aforementioned various epoxy srMt or glycidyl acrylate,
It can also be used in combination with epoxy group-containing vinyl monomers such as glycidyl methacrylate and allyl glycidyl ether.

In addition, as the unsaturated polyester m-fat, for example, it is a reaction product of (-polyol and polycarmenic acid, α,
Unsaturated polyester fat with β-unsaturated bonds and an acid value of 25 or less, styrene, divinylbenzene, α
- Vinyl monomer copolymerizable with unsaturated polyester resins such as methylstyrene, alkyl (meth)acrylate, and ethylene glycol di(/Jl)7 acrylate, (0
Examples include compositions comprising the following components:) a radical polymerization initiator such as dicumyl peroxide and degenerated benzoyl, and (d) an accelerator such as cobalt naphthenate, which is used as necessary.

The high-strength polyolefin fibrous material mixed with these thermosetting resins is a highly crystalline polyolefin, preferably polyethylene, polypropylene, poly-4-methyl-1
- High molecular weight fibrous materials such as intercopolymers of pentene or other α-olefins copolymerized with a small amount of α-olefins, and these am-like materials have low tensile strength at break and tensile elasticity at room temperature. It has excellent physical properties in terms of ratio.

Particularly 1 intrinsic viscosity (135℃, in decahydronaphthalene)
is 45 dt/g or more, density is 0.95 gAIIA1
4 Highly crystalline ethylene with a high boiling point solvent such as 0-dichlorobenzene or decahydronaphthalene or a molecular weight of about 2
000 or less puttyfin wax is mixed and extruded using a screw extruder, the product is immersed in n-hexane etc. to remove the high boiling point solvent or paraffin wax, and further at a temperature within the range of its glass transition point or melting point, When stretched or oriented by 20 times or more, preferably 30 times or more based on the length, a high-strength polyethylene fibrous material exhibiting physical properties such as a tensile strength at break of 0.50 Pa or more and a tensile modulus of 150 Pa or more at room temperature can be obtained. .

However, although polyethylene fibrous materials do not easily become brittle at low temperatures,
Since it is difficult to withstand high temperatures of 120°C or higher, fibrous materials such as polyglobylene or poly-4-methyl-1-pentene are more suitable depending on the application.
The high-strength polyolefin fibrous material obtained in this way is woven into a fiber material that can withstand high temperatures of about 60.degree. C., and is impregnated with a thermosetting resin to obtain a prepreg or a laminate.

Further, a high-strength polyolefin fibrous material is cut into lengths of approximately 5 to 50 cm and uniformly dispersed in a random direction to obtain an SMO (sheet molding compound).

Alternatively, a thermosetting resin can be incorporated into a bundle of high-strength polyolefin fibers. It is also possible to create a one-way gripleg or filament winding.

The amount of impregnation of the thermosetting resin used is generally about 20-70 mm %, preferably about 30-50% by weight of the composition width.

Furthermore, in order to improve the interfacial adhesion between the thermosetting resin and the high-strength polyolefin fibrous material, if necessary, a high-strength polyolefin R4m-like material may be combined with an ethylene-acrylic acid copolymer or an ethylene-vinyl acetate copolymer. Alternatively, a homopolymer or copolymer of ethylene, propylene, 4-methyl-1-pentene, etc. may be coated with a modified olefin thread polymer such as a maleic anhydride graft modified product, or the surface of the fibrous material may be subjected to plasma discharge treatment or It can also be used after corona discharge treatment.

〔Effect of the invention〕

The composition of the present invention, which is composed of a thermosetting resin and a high-strength polyolefin fiber, provides a cured product that is excellent in lightness and mechanical strength, so it can be used as a building material, boat, tank, vehicle, or aircraft. , it can be effectively used as a structural material for leisure equipment (skis, rackets, surfboards, etc.).

〔Example〕

Next, the present invention will be explained with reference to examples.

Reference Examples 1 to 5 Ultra-high molecular weight polyethylene (intrinsic viscosity 8.20 dt/9
) and 61 parts by weight of paraffin wax (melting point 69°C, molecular weight 460) was melt mixed at a resin temperature of 190°C using a screw extruder (20 m diameter, !, /D-20). , the molten material is extruded through a die with an orifice diameter of 1 mm, and the air gap is 10 times.
℃ cold water, and then using a pair of godet mills, a drawing tank (cypress length 40e) with n-decane as a heating medium was
rn-, bath temperature 130° C.) to perform melt spinning and stretching.

The stretching ratio is calculated from the rotation ratio of the godet roll,
Tensile strength at break, tensile modulus, and residual paraffin wax Ut-1 at each stretching ratio were measured by the following methods.

Using an Instron universal testing machine model 1123 (manufactured by Instron), the sample length between the clamps was 100 mm.
11 m, tensile speed 1001 flll/min, room temperature (23°C)
Tensile modulus measured under the conditions of: Dynamic viscoelasticity measuring device 'Vibron DD
Measured at room temperature (23°C) at a frequency of 110 Hs using a V-■ type (manufactured by Toyo Baldwin).The fiber cross-sectional area required for measurement is 0.96 g for the density of polyethylene.
/cII, Jlitaotrxm and the remaining putty fin wax calculated by measuring the length: Soaked in n-hexane for one day and night. The fins were eluted from the fibers and the eluted amount was measured.The measurement results for each of the above items are shown in the following Table IK.

Table 1 1 1G, 0 0.66 18.6 10.
7220゜0 1.02 59.2 5.8
3 25.5 1.2X, 6 & 4 6.
94 30.2 1.34 8'1.3 7
．． 75 35.5 1.40 106.0
6.2 Example 1 Epoxy resin (Mitsui Petrochemical epoxy product Evomic R
-301) 1009, same (company product EvoMitsuku R-
140) 309, dicyamine diamide 4g and N-(
3,4-dichlorophenyl) Hz 3 g of N/-dimethylurea was mixed with methyl ethyl ketone 339 and M,H-
The high i-strength polyethylene fiber multifiber of Reference Example 5 was impregnated with the fabric dissolved in a mixed solvent of dimethylformamide 209, and dried at 100°C for 20 minutes.
A unidirectional prepreg was obtained.

Nine sheets of this prepreg were laminated and press-molded under conditions of 80° C., 8%, and 2 hours to produce a 9-ply unidirectional laminate.

Example 2 The high-strength polyethylene fiber of Reference Example 5 was subjected to plasma treatment for 3 minutes in air at a flow rate of ffi 20 tRt/min and a degree of vacuum of 0.51XmKg. 80 g of epoxy resin (Evomic R-301) and the same (Evomic R-14) were added to this plasma-treated high-strength polyethylene fiber.
0), a fabric prepared from 10.7 g of diaminodiphenylmethane and 73.89 g of methyl ethyl ketone was impregnated and dried at 100° C. for 15 minutes to obtain a unidirectional prepreg.

Nine sheets of this prepreg were laminated and press-molded under conditions of 120° C., 8%, and 2 hours to produce a 9-ply unidirectional laminate.

Example 3 50% of the plasma-treated high-strength polyethylene fiber of Example 2
Cut it to the proverbial length and make it into a mat shape with a basis weight of 0.07 g/i, add 70 g of phenol C-lac resin (Nippon Kayaku IP2N-201) and 30 g of epoxy resin (Epomiku lt-140). , dicyaminediami I'89, N -(3,4-dichlorophenyl)-N'
, N'-dimethyl! ! 47, divinylbenzene 30,
Epoxy (meth)acrylate (Showa Kobunshi Lipoxy H-600) 30'! , benzoyl peroxide 0.3
9, impregnated with a composition consisting of 6 g of polyincyanate (Japan Polyurethane Products Millionate HR-200) and 0.1 g of Dipti/LI tin dilaure);
After pressing at room temperature - leaving the embryo overnight, the SM is about 3cm thick.
It was set as O.

This f9Mo was press-molded at 100° C. for 3 hours to obtain a plate-shaped molded product with a thickness of 20 mm.

Example 4 Polyamino bismaleimide (Kelimide 1oso, manufactured by A-Ne Boulin) 60
g, glycidyl methacrylate 409, dicumyl peroxide Iy, dicyandiamide 29 and 1-sia/
Ethyl-2-ethyl-4-methylimidazole 0.57
This was impregnated with a composition consisting of the following: pressed at room temperature, and then left overnight to form an SMO with a thickness of about 3 mm.

This SMO was press-molded at 160°C for 3 minutes, and then
Post-curing was performed at 00° C. for 24 hours to obtain a plate-shaped molded product with a thickness of 2 mm.

Example 5 The plasma-treated high-strength polyethylene fiber of Example 2 was coated with an unsaturated polyester resin (Showa Kobunshi Product Rivolac 15).
0 HR) 1009, benzoyl peroxide 0.59
, Copal naphthenate) and 2 g of magnesium oxide were impregnated and pelleted at room temperature to give an SMO of approximately 3 IiJI thickness.

This SUO was press-molded at 160°C for 2 minutes to a thickness of 2
A plate-shaped molded product was obtained.

The physical property values shown in Table 2 below were measured for the unidirectional laminates obtained in Examples 1 to 2 and the molded products obtained in Examples 3 to 5.

Table 2

Claims (1)

[Claims] 1. A thermosetting resin composition comprising a thermosetting resin and a high-strength polyolefin fibrous material. 2. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an epoxy resin. 3. The high-strength polyolefin fibrous material has a tensile strength at break of 0.5 GPa or more and a tensile modulus of 15 GPa at room temperature.
The thermosetting resin composition according to claim 1, which is a polyethylene fibrous material having the above physical properties. 4. The thermosetting resin composition according to claim 1, wherein the thermosetting resin is used in the form of being impregnated with a high-strength polyolefin fibrous material.