JPH01252615A - Resin composition - Google Patents

Abstract

PURPOSE:To attempt to form a resin compsn. having low viscosity, rapid curability, and excellent non-tackiness, non-foaming property and moldability and being useful for a resin injection molding process, by compounding a specified unsated. polyester acrylate with methyl (meth)acrylate monomer. CONSTITUTION:The title compsn. is a resin compsn. consisting of 50-70wt.% unsatd. polyester acrylate [I] having (meth)acryalte groups on both terminals of its molecule and a number-average MW of 1,500-3,000 obtd. by reacting an unsatd. polyester having carboxyl groups on both terminals with an unsatd. glycidyl compd. and 30-50wt.% methyl (meth)acrylate monomer [II] and having a viscosity of 3P or lower. The (meth)acrylate content of said acrylate [I] is pref. 8-21wt.%.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a resin composition for fiber-reinforced high-speed injection molding (hereinafter abbreviated as R-RIM molding) used in the resin injection molding method. Low viscosity, fast curing, non-stick,
This invention relates to a resin composition with excellent non-foaming properties and moldability.

[Prior art]

One of the molding methods for fiber-reinforced thermosetting plastics (hereinafter abbreviated as FlζP) is Lennon Indigo! method (hereinafter referred to as R
1 molding method). This molding method allows molding to be performed at low pressure and low temperature, so it has the advantage of reducing mold costs and equipment investments such as pressing.

Therefore, it is attracting attention as a molding method for large molded products.

However, there are problems with moldability and productivity.

[Invention tries to solve! ff1) That is, in order to meet these demands, high-speed injectability and fast curing properties of the resin composition by R-RIM molding method are essential. However, the unsaturated polyester resin compositions produced by conventional techniques have high viscosity (5=2 O voids) and long curing times (10 to 40 minutes), so if the desired productivity cannot be obtained, There were nine problems.Furthermore, the foamability of the molded product,
That is, bubbles are generated on the surface, deteriorating the appearance and decreasing mechanical strength. On the other hand, in terms of workability, there were problems such as residual adhesiveness on the surface of the resin (usually called resin) that flowed out of the mold and contaminating the molded product.

There has been much research into improving unsaturated polyester resins and creating new resin compositions.

For example, vinyl ester urethane found in Japanese Patent Application Laid-Open No. 55-43179.

These resin compositions can be molded in a molding time of 1 minute/m" or less in terms of productivity. However, the problem with the name of the song is that there are many reaction operation steps such as esterification reaction step and urethanization reaction step, and it is difficult to complete the entire reaction. It's a long time.

Furthermore, since an isocyanate component is used as a raw material, there is a problem that residual incyanate, which cannot be confirmed by rIt analysis, deteriorates storage stability.

Furthermore, since the latter is a two-component type, the curing reaction during molding involves the urethanization reaction and the crosslinking reaction of the vinyl single cap, which proceed at the same time, but the reaction rates of both can be arbitrarily controlled and balanced. There are also problems in that it is difficult to do so, and that carbon dioxide is generated and foaming occurs due to the reaction between the isocyanate and the water in at. These phenomena cause problems in molded products, such as poor appearance due to the bubbles) and a decrease in mechanical strength. In addition, there was a problem in that the resin that flowed out of the mold had poor curing properties and remained sticky for a long time, resulting in poor workability.

[Means to solve problems]

Therefore, the present inventors investigated whether the normally used unsaturated polyester acrylate, which does not have a urethane bond, could be used for R-RIM molding without using the vinyl ester urethane that has the above-mentioned problems. As a result of intensive research, a specific resin composition was found to be 10
It can be molded at medium to low temperatures below 0°C, has a viscosity of 3 poise or less at 25°C, has fast curing properties with a curing time of 3 minutes or less, and is non-adhesive and non-foaming. The present inventors have discovered that the present invention is superior and have completed the present invention.

That is, the present invention provides (1) a molecule having a number average molecular weight of 1,500 to 3,000 obtained by reacting an unsaturated polyester having Cal and sil groups at both ends with an unsaturated glycysol compound; ) Acrylic: lt, -1) 50 to 70% by weight of unsaturated polyester acrylate having a group, and @
The present invention provides a resin composition comprising 30 to 50% by weight of methyl (meth)acrylate and a viscosity of 3 poise or less.

〔composition〕

The unsaturated polyester acrylate having (meth)ac 11 L-) groups at both ends of the molecule of the present invention refers to an acid component containing a saturated polybasic acid or its anhydride, and optionally an unsaturated polybasic acid or its anhydride. An unsaturated polyester obtained by reacting an alcohol component and an alcohol component at an equivalent ratio of 2:1, that is, an unsaturated polyester containing carmexyl groups at both ends of the molecule, and an unsaturated glycisol compound added to the unsaturated polyester. It is made of polyester acrylate.

Examples of the unsaturated glycidyl compound which is a component constituting this terester include well-known and commonly used glycidyl esters of unsaturated basic acids such as acrylic acid and methacrylic acid, such as glycidyl 7-nor acrylate and glycidyl methacrylate. Can be done. Incidentally, as such an unsaturated glycidyl compound, glycidyl methacrylate is preferable.

Examples of dibasic acid components include phthalic acid, phthalic anhydride,
Tetrahydrophthalic anhydride, cis-3-methyl-4-
Cyclohexene-cis, cis-1,2-dicarboxylic anhydride, isophthalic acid, terephthalic acid, trimethylterephthalic acid, monochlorophthalic acid, nochlorophthalic acid, trichlorophthalic acid, het acid, tetrabromphthalic acid, cepatic acid, succinic acid Known and commonly used saturated acids such as , anopic acid, glutaric acid, pimelic acid, trimellitic acid, and pyromellitic acid, or their anhydrides or esters can be used. Isophthalic acid is preferred.

In addition, as unsaturated polybasic acids or their anhydrides that may be used in combination if necessary, maleic acid, fumaric acid, itaconic acid,
There are known and commonly used α,β-unsaturated lower group acids such as citraconic acid, methaconic acid, chlorinated maleic acid, etc., or their anhydrides.

Regarding the alcohol component of polyester acrylate,
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, fluoropylene glycol, diglobylene glycol, trif'o pyrene glycol, volip o +"remaglycol, 1.
3-butylene glycol, :), 3. -! Polymer glycol, 1,4-butylene glycol, neo(butylene glycol, hexylene glycol, octyl glycol, trimethylolprozene, glycerin, metaerythritol, hydroquinone with ethylene oxide or haflopylene oxide) Examples include well-known and commonly used polyhydric alcohols such as EO or haPO adducts of bisphenol A, hydrogenated bisphenol A, tricyclodecane) methylol, etc. In particular, glycols with a rigid structure having a bisulf, -nol skeleton are preferred. .

The number average molecular size of this polyester acrylate is 1
500-3000, preferably 1800-2800. If the molecular weight is less than 1,500, the resulting molded product may become sticky or have poor physical properties such as tensile strength, while if it is greater than 3,000, the molding and foaming properties and molding time will be long, resulting in poor productivity. It becomes inferior to.

Unsaturated polyester acrylate (I) in the present invention
is 50 to 70% by weight, preferably 55 to 60% by weight, and if it is less than 50% by weight, the curing properties will be poor and the surface of the resin that flows out of the mold will remain sticky forever. If the thickness is too large, the viscosity will be high, the molding time will be long, and the p-crosslinking density will not be sufficiently high, resulting in poor physical properties such as tensile strength.

In the present invention, methyl nisdel (meth)acrylate σD is used in an amount of 30 to 50 weights, preferably L<40 to 45 weights. This point is also important as above.

The use of (meth)acrylic acid methyl ester in the present invention is particularly important in obtaining fast curing properties (molding time of about 3 minutes).

(Meta)ara 11 of polyester acrylate of the present invention
The content of groups is preferably 8 to 21, especially 1.
0 to 21 layers.

The resin composition of the present invention may optionally include a thickener, a colorant,
reinforcing materials, fillers, curing catalysts, curing accelerators, curing retarders,
An internal mold release agent, a shrinkage reducing agent, etc. may be added.

Thickeners and 12 chemically bond with hydroxyl groups, carmexyl groups, ester bonds, etc. possessed by the resin to form linear or partially cross-linked molecules to increase the number of molecules and thicken the unsaturated polyester resin. For example, diincyanates such as toluene diisocyanate, metal alkoxides such as aluminum isoglopoxide, titanium tetrabutoxy, oxides of metal 2IIIi such as magnesium oxide, calcium oxide, and beryllium oxide, and calcium hydroxide. Examples include hydroxides of 2111il gold such as 9M. The amount of thickener used is usually from 0.2 to 10 parts by weight, preferably from 0.5 to 4 parts by weight, per tootiL parts of unsaturated polyester acrylate. If necessary, it is advisable to use a small amount of a highly polar substance such as water in combination with a thickening agent.

For the colorant and 17, any of the conventionally known inorganic dyes and pigments can be used, but among them, one that has excellent heat resistance and transparency, and does not significantly interfere with the curing of the unsaturated polyester acrylate. is good luck.

The reinforcing material used in the present invention is generally glass l.
Examples include JA fibers, but other examples include organic fibers such as vinylon, bolier, stell, phenol, polyvinyl acetate, polyamide, polyenylene sulfide, and inorganic fibers such as asbestos, carbon fiber, gold IAlltm, and ceramic fibers. However, its shape is silk fabric or non-woven fabric.

Furthermore, the reinforcing material is not limited to fibers, but also includes plastic foams such as polyurethane foam, phenol 7i-me, vinyl chloride foam, and polyethylene foam; hardened media such as glass and ceramics; metals, ceramics, and glass plastics. , solid materials such as concrete, wood, and paper;
Examples include a molded product or a two-cam structure.

Fillers include calcium carbonate powder, clay, alumina powder, crushed stone powder, Merck, barium sulfate, silica powder, glass powder, glass peas, mica, aluminum hydroxide, cellulose thread, silica sand, river sand, kansui stone, astronomical stone. Known materials such as scraps and crushed stone may be used, and among them, glass powder, aluminum hydroxide, sulfuric acid/glyum, etc. are preferable because they provide transparency after curing.

As a curing accelerator, a metal compound is added as necessary, and examples of such metal compounds include cobalt naphtonate, cobalt octonate, divalent acetylacetone copal), cobalt acetylacetone of 31i1fi, potassium hequinate, Zirconium naphtonate, zorconium acetylacetonate, vanadium naphtonate, panasium octonate, vanadium acetylacetonate, vanadyl acetylacetonate,
Metal compound accelerators commonly used in lower ester resins such as lithium acetylacetonate are used;
These may be used in combination, or in combination with other known promoters such as amines, phosphorus-containing compounds, β-diketones, etc.

The amount of the curing accelerator added is appropriately adjusted depending on the gluing time, but it is preferably 0.0001 to 0 as the metal component.
．． 5 parts by weight. This curing accelerator may be omitted or may be used when molding is performed at medium temperature or higher (40° C. or higher).

As a curing catalyst, unsaturated polyester acrylate) K
azo compounds such as azoisobutyronitrile, tert-butyl perbenzoate,
Examples include organic peroxides such as tertiary bar octoate, penzoyl oxide, methyl ethyl ketone peroxide, acetoacetic ester f-oxide, and dicumyl peroxide, based on 100 parts by weight of unsaturated polyester acrylate. 0.1~4
It can be used in parts by weight, preferably in a range of 0.3 to 3 parts.

Preferred are redox curing agents such as acetoacetate mother oxide, cobalt naphthenate, benzoyl peroxide, and dimethyl toluidine.

Examples of the curing retarder include hydroquinone, toluhydroquinone, tert-butylcatechol, copper naphthenate, etc., and it is preferably used in an amount of o, oooi to 0.1 part by weight per 100 parts by weight of the resin composition. Ru.

As the internal mold release agent, conventionally known ones such as higher fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters can be used.
It can be used usually in a proportion of 0.5 to 51 parts per 100 parts by weight of unsaturated polyester acrylate.

The low shrinkage agent is a thermoplastic resin, and specific examples include lower alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate, styrene, vinyl chloride, and acetic acid. Homopolymers or copolymers of monomers such as vinyl, at least one of the vinyl monomers and lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, acrylonitrile, methacrylaterile, Examples include copolymers of at least one monomer consisting of acrylic acid, methacrylic acid, and cetylstearyl methacrylate, as well as cellulose acetate butyrate, cellulose acetate propionate, polyethylene, polypropylene, and saturated polyester. These may be added as necessary and as long as they do not impair the effects of the present invention, depending on the intended use.

The present invention can be cured by heating with the addition of various peroxides, or can be cured with active light such as ultraviolet rays with the addition of various photosensitizers. The cured molded product has extremely few bubbles and excellent mechanical strength.

Incidentally, the number average molecular weight defined in the present invention refers to a value measured using the following measurement method using GPC (permeability chromatography).

GPC: LC-08 type column manufactured by Nippon Analytical Industry Co., Ltd.:
5HODEX A-804+A-803+A-802+
A-801 (Showa Denko Membrane) Solvent: THF Calibration curve preparation standard sample: Polystyrene (Tone-9 products) Detector: Finger refractometer (manufactured by Nippon Analytical Industry Co., Ltd. (a)) According to the present invention,
1 and R-RIM molding using the composition, preferably the mold temperature is 50 to iso°C and the mold pressure is 10 to 100 kg/c.
The injection of the composition is carried out under molding conditions of 10 to 15 m.
Perform at a pressure of 0 kg/(7)2.

The composition of the present invention must have a viscosity of 3 voids or less. This is because it is difficult to use it for R-RIM because it is difficult to inject unless the viscosity at the time of injection is 3 poise or less.

The composition of the present invention usually has a viscosity of 3 poise or less at 25°C, but it does not necessarily have to be 3 poise or less at K, and it can be reduced to 3 I or less by heating or other means during injection, and the effects of the present invention can be achieved. Any composition can be used as long as it can achieve the following.

〔effect〕

The resin composition of the present invention has fast curing properties and low viscosity, and the cured molded product is non-adhesive and non-foaming.
It is extremely superior as a resin composition for M molding. Used as a material for molded products in various industrial fields.

EXAMPLES The present invention will be explained in more detail below with reference to Examples.

Note that "parts" indicate parts by weight.

Reference example-1 [Polyester acrylate] (PEA-1
) Preparation of isophthalic acid 166 mmol (1 mol) and 1-27''.

Pyrene glycol ts2. P (2 moles) was dehydrated by heating at 220° C. for 100 hours in an inert gas stream to obtain a solid with an acid value of 5. This was cooled to 100°C. Next, 196 iP (2 mol) of maleic anhydride was added to the
Dehydration condensation was carried out by heating at 0° C. for 5 hours to obtain a solid content having an acid value of 254. Hydroquinone o, is i!
- added and cooled to 140°C. Next, glycisol methacrylate 284? (2 mol) and heated to 140℃ for 10
After a time reaction, a solid content with an acid value of 10 was obtained.The solid content was dissolved in 508 g of methacrylic acid methyl ester, with a non-volatile content of 60.5% and a viscosity of 0.45% at 25°C. f22, acid value 6.1 and methacrylate group content in solid content
．． 1270 pieces of 3% polyester acrylate were obtained.

Reference elIJ-2C polyester acrylate) (PE
Preparation of A-2)] Isophthalic acid 166? (1 mol) and 1-2f propylene glycol 76y-(1 mol) Bisphenol A 2 mol adduct of ethylene oxide 324iP (1 mol) were dehydrated by heating at 220°C for 155 hours in an inert gas stream to acidify the solid content. I got something with a value of 5. This was cooled to 100°C. Next, 196/- (2 mol) of maleic anhydride was charged and reacted at 200°C for 6 hours to obtain a solid content with an acid value of 163.

To this, 0.21 idokuquinone was added and cooled to 140°C. Next, glycidyl methacrylate 284/(2 mol) was charged and reacted at 140°C for 10 hours, resulting in a solid content of Ii 2 and 8. This solid content was dissolved in methacrylic acid methyl ester monomer 683/ to form a polyester having a non-volatile content of 61%, a viscosity of 2 poise at 25°C, an acid value of 5.8, and a methacrylate group content of 16.896 in the solid content. Acrylate 16B3? I got it.

Reference example-3 [Styrene type polyester acrylate (P
Preparation of EA-3)] The same solid acid content as in Reference Example-2 was dissolved in styrene monomer, and the non-volatile content was 6 os, the viscosity was 10 poise, the acid value was 6.2, and the methacrylate in the solid content was A styrene-soluble polyester acrylate having a group content of 16.8 inches was obtained.

ε Precedent-4 [Polyester acrylate (PEA-4)
Preparation of in7talic acid 166P (1 mol) and 1-2 propionate/
Adduct of glycol 769-(1 mol) and bisphenol A with 2 mols of ethylene oxide 324? (1 mol) was subjected to dehydration condensation under heating at 220° C. for 15 days in an inert gas stream to obtain a solid acid 1111i4. This is 100
Cooled to ℃. Next, maleic anhydride 147i! −(1,
5 mol) was heated and dehydrated and condensed at 200° C. for 6 hours to obtain a solid content with an acid value of 85. Add 0 hydroquinone to this
．． 16 and P were added and cooled to 140°C. Next, add 142 iP (1 mol) of glycidyl methacrylate 14
The reaction was carried out at 0° C. for 10 hours to obtain a solid content with an acid value of 8. This solid content was dissolved in 546 pieces of methacrylic acid methyl ester, and the nonvolatile content was 61.5%, the viscosity was 3 poise at 25°C, the acid value was 4.9, and the methacrylate group content in the solid content was 10. 4% polyester acrylate 1365t
I got it.

Reference example-5 [Polyester acrylate] (PEA-5
)] Isophthalic acid 1331F (0.8 mol), 1-2 propylene glycol 76p (1 mol) and bisphenol A
324 (1 mole) of 2 mole adduct of ethylene oxide of
The mixture was heated and dehydrated in an inert gas stream at 220° C. for 9 hours to obtain a solid with an acid value of 3. This was cooled to 100°C. Next, maleic anhydride 147. P (1.5 mol) was prepared and heated at 200°C for 6 hours to combine with dehydrated cotton to reduce the solid content to 1.5 mol of acid.
I got something called i1fi53.5. To this was added 0.16 g of no-hydroquinone, and the mixture was cooled to 140°C. Next, glycidyl methacrylate) 85P (0.6 mol) was charged and reacted at 140° C. for 6 hours to obtain a solid molecule fiWJlo. This solid content was dissolved in methacrylic acid methyl ester monomer 472/- to give a non-volatile content of 60.2 k, an acid value of 6,
Polyester acrylate 1 with a viscosity of 20 poise at 25°C and a methacrylate x content of 7.2% in solid content
181 iP was obtained.

Reference Examples-6 to 9 [Polyester acrylate (PEA-
Preparation of 6 to 9)] Unsaturated I-lyester acrylate was synthesized in the same manner as in Reference Example 1 according to the formulation shown in Table 1, and dissolved in methacrylic acid methyl ester monomer.

Various properties of the resin compositions obtained in Reference Examples 1 to 9 are listed in Table 1.

Examples-1 to 6, Comparative Examples 1 to 9 Resin PEA-1 obtained in Reference Example-1 as Example-1
An RI test was conducted by blending 50-thipenzoylno-9-oxide and dimethyl para-toluidine in the proportions shown in Table 2. The results are shown in the same table. Further, Examples 2 to 4 and Comparative Examples 1 to 9 were also conducted in the same manner as in Example-1. The various performances were measured by the methods described below.

0 curability:=? - The torque-time curve at 40° C. was determined using a last meter (type 2) (manufactured by Japan Synthetic Rubber Co., Ltd.).

0 Viscosity: Steady flow viscosity needle at 25℃ (Rheometer IR-200 manufactured by Roki Seisakusho) O High speed injection and molding test: 50X100X0.3cW
It was prepared so that the glass content was 50% in the L aluminum mold! After charging the reforming mat, the mold was clamped at 20 kg/12. Inside this mold is KRAUSS-MAFFEI M4.
MIXING - HEAD m RIM Injector K Injected at an injection pressure of 150 kli'/cm''.

At that time, clear the opposite side from the start of injection. Time during which the injected resin liquid flows out of the lance The period up to that point is shown as the injection time.

As is clear from Table 2, Comparative Examples -1, -4, and -5 using unsaturated polyester acrylates in which the number average molecular needle of the present invention has been removed have physical properties such as tackiness and tensile strength, and fast curing properties. It was inferior to Furthermore, Comparative Examples-2 and -3 in which the monomer was dissolved in styrene instead of methyl methacrylate monomer were inferior in fast curing properties, foaming properties, adhesiveness, and physical properties. Moreover, Comparative Examples-8 and -9, which were outside the composition range of the present invention, were poor in fast curing properties, adhesiveness, physical properties, etc.

- The strength wood composition of the invention was excellent in low viscosity, low-temperature fast curing properties, and moldability.

/ ・'2ノ (Note) ■6 Copal chinapthenate): 0.1 (N)■
Nobutyltin (benzony): 0.1 ■ Tertiarybutyltin (benzony): 2.6 ■ Diphenylmethane soisocyanate: 51.1 Agent: Katsutoshi Takahashi, patent attorney

Claims (1)

[Claims] 1. (I) Unsaturated polyester acrylate 50 having (meth)acrylate groups at both ends of a molecule with a number average molecular weight of 1500 to 3000 obtained by reacting an unsaturated polyester having carboxyl groups at both ends with an unsaturated glycidyl compound 70% by weight, and 30-50% by weight of (II) (meth)acrylic acid methyl ester monomer, and has a viscosity of 3 poise or less.