JPH04175328A - Resin-forming composition - Google Patents

Abstract

PURPOSE:To obtain a composition which can form a resin having high rigidity and high heat resistance by mixing a mixture of three compounds each of which has at least one polymerizable vinyl group and at least one hydroxyl group and which have different molecular weights with a polycyclic organic polyisocyanate, a urethane formation catalyst and a radial polymerization catalyst. CONSTITUTION:A resin-forming composition is prepared by mixing a mixture (A) of three compounds each of which has at least one polymerizable group and at least one hydroxyl group and which have molecular weights of below 230, 230-2,000 and 2,000-20,000, respectively, in a ratio of (85-55):(10-25):(5-20) with a polycyclic polyisocyanate (B) (e.g. diphenylmethane diisocyanate), a urethane formation catalyst (C) (e.g. an amine catalyst or a tin catalyst) and a radical polymerization catalyst (D) (e.g. azoic or peroxide catalyst). The mixing ratio among the respective components is such that the isocyanate index (NCO/OH equivalent ratioX100) is 20-200, particularly 70-110, and 0.001-5% component C and 0.1-5%, preferably 0.5-3% component D are present.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to urethane resin-forming compositions.

More specifically, the present invention relates to a urethane resin-forming composition capable of producing a hard urethane with high rigidity and excellent heat resistance.

[Prior Art] Conventionally, glass fiber reinforced polyester resins (FRP), urethane resins containing fillers such as glass fibers, epoxy resins, etc. are known as resins with high rigidity and excellent heat resistance.

[Problems to be solved by the invention] However, the conventional resins exemplified above have strong odor from components such as polymerized monomers, long curing times, poor flexibility in molding shape, and poor rigidity and heat resistance. There were problems such as a lack of.

[Means for Solving the Problems] The present inventors solved these problems and, as a result of intensive studies to obtain a composition capable of forming a resin having high rigidity and high heat resistance, arrived at the present invention. did.

That is, the present invention is a mixture of compounds each having one or more polymerizable vinyl groups and one or more hydroxyl groups and having different molecular weights, and having a molecular weight of less than 230, from 230 to less than 2000, and from 200 to less than 200.
0 to 20,000 in a weight ratio of 85 to 55:10
~25: A mixture (a) of compounds having the formula 5 to 20, a polycyclic perforated polyisocyanate (b), a urethanization catalyst (c), a radical polymerization catalyst (d), and optionally a radical polymerization promoter ( A urethane resin-forming composition characterized by comprising a combination of (e) and (e). In the present invention, the compound having one or more polymerizable vinyl groups and one or more hydroxyl groups is, for example, based on vinyl group-containing organic acids such as acrylic acid, methacrylic acid, tiglic acid, and 2-pentenoic acid, and polyhydric alcohols. , and compounds obtained by reacting alkylene oxide adducts of polyhydric alcohols. Among these vinyl group-containing organic acids, (meth)acrylic acid is preferred. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, 1, 3-, and 1-I.

Alkylene glycols such as 4-butanediol, I,6-hexanediol, neopentyl glycol, and diols containing a cyclic group (for example, Japanese Patent Publication No. 45-1
Dihydric alcohols such as those described in Publication No. 474); Trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol, and triethanolamine; Tetrahydric alcohols such as pentaerythritol, methylglyfusitol, and diglycerin;
Adonitol, arabitol.

Pentitol, sorbitol such as quinlitol.

Hexitols such as mannitol, iditol, talitol, and zurntol; Monosaccharides such as glucose, mannose, fructose, and sorbose; Polysaccharides such as sucrose, talehalose, lactose, and raffinose; Polyols (e.g., glycols such as ethylene glycol, propylene glycol, and glycerol) , alkane polyols such as trimethylolpropane and hexanetriol); polyglycerols such as triglycerin and tetraglycerin; dipentaerythritol.

Examples include polypentaerythritol such as tripentaerythritol; cycloalkane polyols such as tetrakis(hydroxymethyl)cyclohexanol.

Examples of the alkylene oxide constituting the alkylene oxide adduct include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO),
1.2- or 1.4-butylene oxide,
Examples include styrene oxide, etc., and a combination of two or more of these (in this case, block and/or randomly added polyalkylene oxide). mixture (a
) is a compound having at least one polymerizable vinyl group and one or more hydroxyl group as exemplified above, and is composed of a mixture of compounds having different molecular weights. The ratio according to the molecular weight of each compound in (a) is 2
less than 30, 230 to less than 2000 and 2000 to 20
The weight ratio of each of the 000 compounds is usually 85 to 55:10.
~25: 5 to 20. Note that two or more types of compounds having each molecular weight may be used.

Preferable compounds having a molecular weight of less than 230 and from 230 to less than 2000 are, for example, mono- or di(meth)acrylates of glycerin, poly(meth)acrylates of glycerin, pentaerythritol, sorbitol, sugar, or alkylene oxide adducts thereof. Examples include those having a molecular weight of 230 to 2,000. Preferred compounds having a molecular weight of 2,000 to 20,000 include compounds obtained by further adding an alkylene oxide to the alkylene oxide adducts mentioned above with a molecular weight of 230 to 2,000 to increase the molecular weight, and these compounds and (meth) It is a reaction product with acrylic acid. Molecular weight 2
If the weight ratio of the compound is less than 30 and exceeds 85, it is difficult to impart high rigidity and high heat resistance while having appropriate flexibility, and if the weight ratio is less than 55, the molecular weight increases relatively.
Compounds with a molecular weight of 0 to less than 2,000 result in poor flexibility. If the number of compounds having a molecular weight of 230 to less than 2,000 is less than 10, high rigidity and high heat resistance will be insufficiently imparted, and if it exceeds 25, flexibility will be insufficiently imparted, making it impossible to obtain the characteristics of the present invention. In addition, compounds with a molecular weight of 2,000 to 20,000 are
If it is less than 20, the flexibility of the resin composition will be insufficient, and if it exceeds 20, it will be impossible to obtain a resin with high rigidity and high heat resistance.

As the polycyclic organic bodiisocyanate (b) used in the present invention, for example, 2,4'-
and/or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI (crude diaminophenylmethane [condensation product of formaldehyde and aromatic amines (anilines) or mixtures thereof], or diaminodiphenylmethane and small amounts (e.g. 5-20 wt. %)
phosgenates); and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretdione groups, uretonimine groups, incyanurate groups) , oxazolidone group-containing modified products, etc.). Among these, preferred are 4,4'- and /
or 2,4′-MDI, crude MDI,
Also, polyisocyanates modified with a urethane group, a carbodiimide group, an allophanate group, a urea group, a piure, a to group, or an isocyanurate group derived from these polyisocyanates.

The ratio of components (a) and (b) in the resin-forming composition of the present invention is determined by the following iso/anate index [[010H equivalent ratio×
! Adjust so that it becomes 00. That is, the isonoanate index is usually 20 to 200. Preferably 50-I30
．． Particularly preferably 70 to +10. However, if polyisocyanate groups are introduced into the polyurethane, the isonoanate index may be significantly higher than the above range (for example, 300-1000 or more).

In the present invention, the urethanization catalyst (c) is a catalyst commonly used in polyurethane reactions to accelerate the reaction [e.g., amine catalysts (tertiary amines such as triethylene diamine, tetramethylhexamethylene diamine, etc.), tin catalysts, etc. (stannous octylate, dibutyltin dilaurate, etc.) and other metal catalysts (lead octylate, etc.). The amount of catalyst (c) is used in small amounts, usually from about 0.001 to about 5%, based on the weight of the composition of the invention.

In the present invention, the radical polymerization initiator (d) includes, for example, azo compounds, peroxide compounds, and peroxides other than those described in JP-A-61-76517,
Alternatively, persulfates, perborates, etc. may be mentioned. As a specific example of the polymerization initiator (d), an azo compound such as "Aso Nerine Reduction Initiator" manufactured by Wako Pure Chemical Industries, Ltd. may be mentioned. As peroxide compounds, for example, "Journal of the Japan Society for Composite Materials 41990 Vol. 16 No. 4 P, 1
Examples include those described in Nos. 32 to 138. Among these, preferred is 2,2'-asobis (2,4-asobis).
2.2'-Asobisisobutylperoxybensoate, Hose(4-tert-butylcyclohexyl).

-Oxycarbonate and the like. The amount of the polymerization initiator (d) used is 0.1% to 5%, preferably 0.5x to 3%, based on the compound or mixture having a vinyl group and a hydroxyl group in the molecule.

In addition, in the present invention, the radical polymerization accelerator (e) to be used if necessary is as described in "FRP Molding Processing Technology" published by Kogyo Kenkyukai, P. Examples include those listed in Table 28 of No. 36. Preferred in this table are cobalt naphthenate and cobalt octoate. Polymerization accelerator (e
), the amount used should be the same as the above-mentioned polymerization initiator (
The same usage amount as in d) is sufficient. Further, the composition of the present invention may contain other additives if necessary. As an additive, a blowing agent (for example, methylene chloride, water, an alternative fluorocarbon compound, etc.) can be used. The amount of blowing agent used depends on the desired density of the polyurethane (e.g. 0.05-1,
4g/am3). Surfactants such as antifoaming agents and foam stabilizers can also be used. In addition, reinforcing materials, flame retardants, reaction retarders, colorants, internal mold release agents, anti-aging agents,
Known additives such as antioxidants, plasticizers, bactericides, and fillers such as carbon black can also be used. Among them, the reinforcing material is an additive that is particularly effective in imparting high rigidity and high heat resistance in the present invention.Continuous glass fibers or those processed into a woven fabric are commonly used. Can be mentioned.

The composition of the present invention usually consists of two liquids, A and B. For example, the A component includes (a) and (c) obtained in the present invention.
) and (e), and the B component is a mixture consisting of (b) and (d). The method for producing molded articles from the resin-forming composition of the present invention is usually carried out by the Wanyonoto method. be able to. For this molding, an ordinary machine for producing urethane foam (generally called a foaming machine) can be used. This foaming machine mostly consists of a tank for storing divided raw materials of 2 to 6 components and a mixing head for mixing them, and has a mechanism that can continuously introduce each raw material into the mixing chamber. The above two liquids A and H are mixed in this mixing head. The equipment used for manufacturing includes the above-mentioned I, low-pressure R organic which is often used for foaming urethane foam, high-pressure foaming machine used for manufacturing urethane bumpers, and spray machines used for other purposes. Various non-foamed or foamed resin compositions can be manufactured by using a liquid mixer to inject or pour into a closed mold or an open mold, and in the case of an open mold, close the lid and proceed with reaction curing. .

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Note that parts and % represent parts by weight and % by weight, respectively. The composition of the raw materials used in Examples 1 to 7 and Comparative Examples 8 to 11, and the equipment and conditions used for evaluation are as follows, and Table 1
Molded articles of each Example and Comparative Example were obtained using the compounding ratio and conditions shown below. Table 1 shows the results of measuring the physical properties of the obtained molded article using the following physical property measuring method. A compound having at least one hydroxyl group and one or more polymerizable vinyl groups is hereinafter abbreviated as vinyl vinylol.

[Raw material used [A] Polyvinyl polyol 1 with a molecular weight of less than 230 Polyvinyl polyol 1 with a molecular weight of 130 obtained by reacting 1 mole of acrylic acid with 1 mole of brobylene glycol.

Polyvinyl polyol 2: Polyvinyl polyol with a molecular weight of 200 obtained by reacting 2 moles of acrylic acid with dry lycerin I.

Polymethylpolyol 3; Molecular weight: 22 obtained by reacting 2 moles of methacrylic acid with 1 mole of phosphoryl
8 Holy Little Little.

[B) Woodenyl glycol 4 having a molecular weight of 230 to less than 2000; Polyvinyl glycol 4 having a molecular weight of 298 obtained by reacting 3 moles of acrylic acid with 1 mole of hephthaerythritol.

Neylene vinylene 5: Neylene vinylene with a molecular weight of 1160 obtained by reacting 1 mole of polyether polyol with a molecular weight of 1000 obtained by reacting pentaerythritol with PO and 3 moles of acrylic acid. Riolu.

Nelyl glycol 6; to solhydritol
Nearyther polyol with a molecular weight of 980 was obtained by reacting 1 mole of a polyether polyol with a molecular weight of 700 obtained by reacting PO with 5 mols of acrylic acid.

Vinyl book Lior 7: To Solhitol P
Polyether polyol (PO/EO: 7/3) with a molecular weight of 13110 was obtained by reacting O and EO.

Ne° Rihi Ni! 1*' Riolu 8;
Molecular weight obtained by reacting P O and EO
Holiether Polyol (PO/EO: 8/
2's 7-rly type*'! Molecular weight +300 obtained by reacting 1 mole of H-yl°9#-le with 6 moles of acrylic acid
Nelehynylpolyol.

[C] Nerihi” with a molecular weight of 2000 to 2θ000
NylboliolVorivinylpolyol 9;
Polyether polyol with a molecular weight of 3,100 obtained by reacting 1 mole of a polyether polyol with a molecular weight of 3,000 obtained by reacting phosphorus with PO and 2 moles of acrylic acid.

Nelyvinylpolyol 10; PO in glycerin
Molecular weight 610θ obtained by reacting 2 moles of polyether t-PIt with 2 moles of methacrylic acid, which was obtained by reacting with EO to give a molecular weight of 5000.
of vinylyl polyol.

Nerich'nyl polyol 1 1; 1 mole of polyethyl polyol, which was obtained by reacting polyol with PO to give a molecular weight of 15,000 and then reacting with EO to give a molecular weight of 17,000, and 5 moles of acrylic acid. A polyvinyl polyol with a molecular weight of 17,300 was obtained.

Organic isocyanate 1; Millionate MR (manufactured by Nippon Polyurethane) Organic isocyanate 2; Sumishil
-L PC (manufactured by Sumitomo Bayer Urethane) Organic isocyanate 3; Millionate MTI, (manufactured by Nippon Polyurethane) urethanization catalyst 1; DABCO33LV (Sankyo Air) (manufactured by Rotact) urethanization catalyst 2; TJ
catlooo (manufactured by NAFKUCHI) 2,2'-Aso'bis (2,4-methylhydronitrile) Gold catalyst 2; Radical polymerization catalyst 3;
Hythus (4-tanyazyphylchlorohexynol)
Hyper-ocylene carbonate) Rancal polymerization accelerator H; Cobalt naphthenate trancal polymerization accelerator 2; Cobalt octoate reinforcing material
; Gontainure Square Maputo After cutting 300g/m2 fabric into a molded knife, use the number of sheets shown in Table-1 by adding t1 to the molding l-'.

[Equipment used for evaluation and its conditions ・Evaluation equipment;
High-pressure foaming machine: llIc-102 (manufactured by Neurethane Ennornia Link) Discharge amount: Approximately 150 g/sec Discharge pressure: 130 to I [10 Kg/cm2 Raw material temperature: A component 25 ± 2 ° CB component 20
±2°C Ison-A-Fert Index: 105 Mold: 301. (l x 400 x thickness 5 n+
m□ External mold release agent: Rimurikei D-18Ei (Middle East Oil 1) [Physical property measurement method] Density (g/am3):
JIS K-6401 bending 1 lath (
Kg/cm2): JIS K
-6911 Bending strength (Kg/cm2):
JIS KJ911 No. 25
mm x 70 mm x thickness 2.5 mm;
40+nm1 Punch diameter; 5R pressurization degree; 2
a+m/min Heat distortion temperature: JIS K-7207 Isosoft impact test: JIS K-71
10 [Effects of the Invention] Compared to conventional methods, molded products using the resin-forming composition of the present invention have higher rigidity and heat resistance, as well as appropriate flexibility of the resin. This makes it possible to produce high-performance resins that combine both high design and high productivity through integral molding of complex-shaped objects, which is a major requirement. Because it exhibits such effects, the resin-forming composition of the present invention can be used as interior materials for automobile doors, instrument panels, rear wheels, etc., and can be used as interior materials for automobile doors, instrument panels, etc. It can be applied to many resin molding fields, such as exterior materials or structural members for home appliances, and the front parts of home appliances.

Patent applicant: Sanyo Chemical Industries, Ltd.

Claims (1)

[Scope of Claims] 1. A mixture of compounds each having one or more polymerizable vinyl groups and one or more hydroxyl groups and having different molecular weights, and having a molecular weight of less than 230, from 230 to less than 2,000, and from 2,000 to 20,000.
The weight ratio of each compound is 85-55:10-25:5-2
0, a polycyclic organic polyisocyanate (b), a urethanization catalyst (c), a radical polymerization catalyst (d), and if necessary a radical polymerization promoter (e
) A urethane resin-forming composition comprising a combination of 2.Claim 1, wherein (a) is a mixture of (meth)acrylic compounds each having one or more polymerizable vinyl groups and one or more hydroxyl groups.
The resin-forming composition described.