JPS62267355A - Low-shrinking agent and low-shrinking thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide a low-shrinking agent for use in thermosetting resin, consisting of a lactone polymer prepared by reaction between an aliphatic oxycarboxylic acid, an ester from polyhydric alcohol and aromatic polybasic acid (anhydride), and epsilon-caprolactone. CONSTITUTION:The objective low-shrinking agent consisting of a lactone polymer with a mol.wt. 1,000-10,000 prepared by reaction, catalysed by titanium compound, pref. in an inert gas atmosphere, between (I) 10-40wt% of (i) 50-90wt% of an aliphatic oxycarboxylic acid (pref. glycolic acid, oxycaproic acid plus (ii) 10-50wt% of an ester from polyhydric alcohol and aromatic polybasic acid (anhydride) and (II) 60-90wt% of epsilon-caprolactone. The other objective composition can be obtained by incorporating (A) 100pts.wt. of a blend of (1) 30-80pts.wt of an unsaturated polyester resin and (2) 70-20pts.wt of an ethylenic unsaturated monomer (e.g. styrene) with (B) 5-200pts.wt of said low-shrinking agent and (C) inorganic filler, reinforcer, and polymerization initiator.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a low-shrinkage agent used for thermosetting resins such as unsaturated polyester resins, and a low-shrinkage agent characterized by using the same low-shrinkage agent. The present invention relates to a thermosetting resin composition.

(Conventional Art) Unsaturated polyester resin compositions have a high dimensional shrinkage rate upon curing (for example, 10X), and therefore molded products obtained from the resin by mold molding, injection molding, etc. may suffer from distortions, cracks, sink marks, etc. There are disadvantages such as the occurrence of molding, lack of smoothness on the surface of the molded product, and embossment of the reinforcing comb used for molding.

In order to eliminate these drawbacks, various studies have been conducted in recent years, such as the invention disclosed in Japanese Patent Application Laid-open No. 48-34289, in which anti-shrinkage materials such as polystyrene, polymethyl methacrylate, etc. are added to unsaturated polyester resins. By mixing and curing thermoplastic polymers, it is possible to produce moldings with virtually no curing shrinkage, and the above-mentioned drawbacks have been considerably improved.

(Problems to be Solved by the Invention) However, ordinary anti-shrinkage plastic polymers such as polystyrene and polymethyl methacrylate have low dispersion stability in unsaturated polyester resin compositions, and the mixture is If left for 5 hours), the polymer floats to the top of the composition, and it also has poor compatibility with fillers and other inorganic fillers, resulting in poor dispersibility.

In order to improve these drawbacks, low shrinkage agents made of lactone polymers having various terminal groups have been proposed.

However, when a highly crystalline lactone polymer is used as a low-shrinkage agent, it has poor solubility in the styrene monomer used at the same time. It had the disadvantage of whitening.

As a result of intensive study by the present inventors to improve this drawback,
By reacting a fatty acid oxycarboxylic acid, a polyhydric alcohol, and an ester compound consisting of an aromatic polybasic acid or its acid anhydride at a certain ratio, and reacting this with ε-caprolactone to form a lactone polymer, styrene can be produced. The present inventors have discovered that solubility is improved, and that by using carbon black as a pigment to make a black molded product, a molded product with less whitening phenomenon can be obtained as well as a good molded product with almost no shrinkage.

(Structure of the Invention) In other words, the present invention provides f(1)a) flh rib group oxycarciboxylic acid 50-9
0 weight percent b) Ester of polyhydric alcohol and aromatic pot FA base acid or its anhydride - 10-50% by weight Total f of a) and b) 1.10-40% C) ε-caprolactone 90-60Φ % and an average molecular weight of 1,000 to 10,000 and r (2) A') unsaturated polyester resin 30 to 80
Heavy ω part B) Ethylenically unsaturated monomer 70 to 20 weight part e) a) Aliphatic oxycarboxylic acid 50 to 90% by weight b) Polyhydric alcohol and aromatic polybasic acid or its anhydride A low-shrinkage agent 5 consisting of a lactone conjugate having an average molecular weight of 1000-10000, consisting of ester 10-50% by weight, total strength of a) and b) 10-40% C) ε-caprolactone 90-60% by weight -200 parts by weight O) 40-400 parts by weight of inorganic filler E) 10-200 parts by weight of reinforcing material F) Low-shrinkage thermosetting polymerization initiator consisting of 0.01-5 parts by weight "Resin composition"
It is.

As the aliphatic oxycarboxylic acid used as component a) in the present invention, glycolic acid, oxycaproic acid, 12-hydroxystearic acid, and hydroxypivalic acid are suitable; ，
It also includes monoesters of aliphatic polyhydric alcohols and aliphatic polybasic acids or anhydrides thereof, each having a structure containing one -COOH. .

The aliphatic polyhydric alcohols in this case are ethylene glycol, diethylene glycol, 1.3 propanediol, 1
．． 4-butylene diol, 1.5bentanediol, 1
, 6 hexanediol, 1゜2 propylene glycol,
1,3-butylene glycol, neopentyl glycol, hydroxypivalic acid ester of neopentyl glycol, 2-methyl-1,3 propanediol, 2.3.
5-trimethylbentanediol, trimethylolpropane, trimethylolethane, etc. can be used.

Examples of aliphatic polybasic acids or their anhydrides include succinic acid,
Examples include maleic acid, fumaric acid, adipic acid, sepacic acid, azelaic acid, dodecanedioic acid, succinic anhydride, and maleic anhydride, and these can also be used in combination.

In addition, the polyhydric alcohols used in the ester of polyhydric alcohol and aromatic polybasic acid or its acid anhydride, which is component b) of the present invention, are ethylene glycol, diethylene glycol, 1.3-propanediol, 1. 4-butylene diol, 1.5bentanediol, 1.6 hexanediol, 1,2 propylene glycol, 1.3-butylene glycol, neopentyl glycol, hydroxypivalic acid ester of neopentyl glycol, 2-methyl-1
, 370 pandiol, 2.3.5-trimethylbentanediol, trimethylolpropane.

Trimethylolethane or the like can be used.

As the aromatic polybasic acid or its anhydride, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, or their anhydrides can be used.

ε-caprolactone, component C) of the present invention, is industrially produced by oxidizing cyclohexanone with a peracid such as hydrogen peroxide or peracetic acid by Bayer-Billiker reaction, and is commercially available.

In the present invention, it is necessary to contain 60 to 90% by weight of ε-caprolactone in the resin, which is a low shrinkage agent.

If ε-caprolactone is less than 60% by weight, the effect as a shrinkage reducing agent will not be exhibited, and if it is more than 1% by weight, polycaprolactone will have poor compatibility with styrene due to its crystallinity. .

The charging ratio of ester of oxycarboxylic acid/polyhydric alcohol and aromatic polybasic acid or its anhydride is ester of oxycarboxylic acid/polyhydric alcohol and aromatic polysalt FiHQ or its anhydride = 515 to 9/1 (weight ratio).

The charging ratio of ester of oxycarboxylic acid/polyhydric alcohol and aromatic polybasic acid or its anhydride is 50% or less of ester of polyhydric alcohol and aromatic polybasic acid or its anhydride to oxycarboxylic acid. If the carbon black is 90% or more, it will not be effective as a shrinkage reducing agent, and if carbon black is used as a pigment to make a black product, a whitening phenomenon will occur, impairing the marketability.

Here, the ester d synthesis of a polyhydric alcohol and an aromatic polybasic acid or its anhydride is carried out as described below.

0.8 ~ phthalic anhydride to diethylene glycol
When the mixture was charged into a 1.2 times reaction flask and the reaction temperature was raised, the flaky phthalic anhydride and diethylene glycol melted at 120-130°C.

The reaction begins.

The reaction humidity is further slowly increased to 150 to 170°C over 2 to 3 hours.

The sudden heating is due to the reaction heat of phthalic anhydride, and the reaction temperature is 200℃.
It is not preferable because it may exceed the color of the product and color the ￥J product.

The reaction temperature is maintained at 150-170°C and the reaction is continued for 4-6 hours.

To determine the end point of the reaction, the concentration of diethylene glycol in the reaction solution is measured using a gas chromatograph, the remaining amount is determined, and the reaction is terminated when the concentration of diethylene glycol is in the range of 17 to 32%.

When the concentration of diethylene glycol is lower than 21%, the esterification reaction progresses too much and dehydration begins.

Further, if it is more than 24%, unreacted phthalic anhydride remains, which is not preferable. In the present invention, instead of component C) ε-caprolactone, oxycaproic acid, which is a ring-opened product thereof, can also be used.

Moreover, other lactones can also be copolymerized.

Next, a method for synthesizing the lactone polymer, which is the low shrinkage agent of the present invention, will be described.

The most basic method is to first synthesize a monoester or polyester polyol (component (b)) with a terminal hydroxyl group and a terminal carboxylic acid from a polyhydric alcohol and an aromatic polybasic acid. Carbon M,
A lactone polymer is synthesized by charging a predetermined amount of c) component ε-caprolactone and carrying out ring-opening polymerization.

Furthermore, oxycarboxylic acids and polyhydric alcohols.

Simultaneously prepare aromatic polybasic acid and ε-caprolactone 9
It can also be synthesized by reacting 6. The reaction temperature is 130°C to 240°C, preferably 140°C to 240°C.
The temperature is 230°C.

Also, passing an inert gas during one reaction gives good results on the color of the resin.

This reaction uses caprolactone ring-opening reaction catalysts such as titanium compounds such as tetrabutyl titanate and tetrapropyl titanate, dibdeltin laurate, octyltin, dibutyltin oxide, stannous chloride, and stannous bromide. , 0.01 to 50 pplIl of tin-colloid, etc.
In particular, it is preferable to use 0.1 to 10 ppm.

Furthermore, among these catalysts, titanium-based compounds in particular exhibit sufficient catalytic activity for transesterification reactions.

The average molecular weight of the lactone polymer obtained in this way is
1000 to 10000.

If it is less than 1,000, the effect as a shrinkage reducing agent is insufficient, and if it is more than 10,000, the viscosity is higher than t.

This is disadvantageous when used in combination with a curable resin.

The molecular vessels can be adjusted by adjusting the reaction molar ratio of the polyester polyol synthesized from components a) and b) and ε-caprolactone.

Another object of the present invention is to provide a thermosetting resin composition such as an unsaturated polyester resin that has excellent low shrinkage properties.

The unsaturated polyester resin as the component (A) used in the low-shrinkage thermosetting resin composition of the present invention is made of α,β-unsaturated dibasic acids and glycols, or if necessary, a saturated dibasic acid is used in combination. Manufactured by

As the α,β-unsaturated dibasic acid, maleic anhydride, maleic acid, fumaric acid, mesaconic acid, tetraconic acid, itaconic acid, chlorinated maleic acid, etc. are used.

Saturated dibasic acids include orthophthalic acid, phthalic anhydride,
inphthalic acid, terephthalic acid, tetrahydrophthalic acid,
Examples include halogenated phthalic anhydride, and esters thereof may also be used.

Glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, and hexylene glycol.

Hydrogenated bisphenol A, 2,2-di(4-hydroxybroboxyphenyl)propane, clove renoxide. Propylenoxide and the like are useful.

The ratio of α, β-unsaturated dibasic acid in the component is 50
If it is less than mol%, the desired low shrinkage effect cannot be obtained sufficiently, so the α,β-unsaturated dibasic acid should be in the range of 50 to 100 mol%, especially in the case of sheet molding compounds. A score of 100% is excellent.

For producing unsaturated polyester, known production methods such as a dissolution method, a solution method, and an epoxy method are used.

Unsaturated polynisal has a molecular ff of 11,000 to 3°00.
0, an acid value of 10 to 50, and a hydroxyl value of 5 to 60.

The ethylenically unsaturated monohung body of component (B) of the present invention is 1
It is an unsaturated monomer having at least one ethylenic double bond in the molecule.

This unsaturated monomer must be capable of crosslinking and thermosetting by reacting with the unsaturated polyester (A), and is preferably one that can dissolve the unsaturated polyester (A).

Specific unsaturated monomers (B) include, for example, styrene, vinyltoluene, lower alkyl esters of acrylic acid or methacrylic acid (for example, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate). , propyl acrylate, butyl methacrylate, butyl acrylate, methacrylic lI!
22'-ethylhexyl, 2-ethylhexyl acrylate), methacrylic acid, acrylic acid, divinylbenzene,
Chlorostyrene, α-methylstyrene, diaryl phthalate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 2,5-dichlorostyrene, 2,5-dipromostyrene, pentapro-7phenol allyl ether, tribromophenyl acrylate, dialkylphosphone Examples include acid, antimony trioxide, diallylbenzenephosphonate, tricresyl phosph, T-t, triallyl phosphate, diallyl ethyl phosphate, methyl β-methylethyl)phosphonoacrylate, (diallylphosphonomethyl)ether, etc. However, styrene is mainly used.

Of course, each of these monomers is not only one type, but also two types.
A mixture of more than one species can also be used.

Examples of the non-solid filler of component (D) include silica, alumina, metal oxides such as iron oxide, zinc oxide, and magnesium oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide; iron; powder, metal powder such as aluminum powder: Other examples include asbestos powder, glass powder, calcium carbonate, magnesium carbonate, sodium sulfate, silica frozen earth, etc.
Chopped slants and glass fiber mats with fiber lengths from 3 to 25M are excluded).

Particle size is 0.1-100μ9. Preferably the particle size is 30μ
The following are good.

Moreover, among these, the use of metal hydroxides has the advantage that the viscosity of the resin composition is low.

(E) As a reinforcing material, glass! fiber, carbon fiber, asbestos, potassium butanate, whiskers, gold E
There are fibers, etc. The fiber length used is 3 to 25 fibers.

In addition, as the polymerization initiator for component (F), benzoyl peroxide, lauryl peroxide, methyl ebulketone peroxide, dicumyl peroxide, 2,5-di(
Peroxides such as peroxybenzoate), tert-butyl perbenzoate, and azo compounds such as azobisisobutyronitrile and dimedyl azodiisobutyronitrile can be used.

Next, the composition of each component will be described.

Component (A) is 30 to 80 parts by weight of unsaturated polyester, and component (B) is 70 to 20 parts by weight of ethylenically unsaturated polyester.
Weight means parts, where A L+ (B') is used in an amount of 100 parts by weight.

(If A> is less than 30 parts by weight, the cured product will not have practical strength.

Moreover, if it exceeds the 80 ω portion, the viscosity will be high and it will be difficult to scoop it out, and the strength will also be weak.

The lactone polymer as the component (C) of the present invention, which is a low-shrinkage agent, is used in an amount of <5 to 100 parts by weight of the unsaturated polyester as the component A) and the ethylenically unsaturated monomer as the component (B). 2
It is used at a ratio of 00 parts by weight, preferably 10 to 100 parts by weight.

If it is less than 5 parts by weight, the shrinkage reduction effect will not be sufficient.

Furthermore, if the amount exceeds 200 parts by weight, the mechanical strength of the cured product will decrease.

The inorganic filler as component (D) is used in an amount of 40 to 400 parts by weight, preferably 50 to 300 parts by weight per 100 parts by weight of components (A) and (B).

If it is less than 40 parts by weight, there is no effect of preventing uneven coloring.

Moreover, if the mechanical strength of the cured product exceeds 400, the mechanical strength of the obtained cured product is not practical.

The reinforcing material of component (E) is the sum of component (A) and component (B) 10
10-200 IU parts to 0 parts by weight.

It is preferably used in a proportion of 30 to 100 parts by weight.

If it is less than 10 parts by weight, there will be no reinforcing effect, and if it exceeds 2001 M parts, the strength of the obtained cured product will decrease.

The polymerization initiator of component (F) is suitably m, generally 0 of component (A).
．． It is used at a ratio of 0.01 to 5% by weight, preferably 0.5 to 2% by weight.

In addition to these components, silane coupling agents, silane coupling accelerators, anti-aggregation agents, polymerization inhibitors, thickeners, pigments, lubricants, etc. may be added.

In order to prepare the resin composition of the present invention, component (A) and (B
) to a commercially available polyester resin containing the components (C),
Components (D), (E) and (F) may be mixed simultaneously.

(Effects of the invention) (a) The novel lactone polymer, which is a low-shrinkage agent of the present invention, is a low-shrinkage agent for unsaturated polyesters and epoxy resins,
It can be extremely advantageously used in many fields, such as surface modifiers, plasticizers for thermoplastics, pigment dispersants, fletane pigment dispersion improvers, paint flexibility imparters, and pigment dispersants.

(b) The unsaturated polyester resin composition blended with the low-shrinkage agent of the present invention prepared in this way has excellent storage stability, and has a shrinkage rate of about +0.05 to ←0.1 part (swelling ), it is possible to give a smooth cured product with no uneven coloring.

Next, the present invention will be explained with reference to synthesis examples and examples.
The present invention is not limited to these.

In addition, in all cases, the ``small'' indicates the part.

Synthesis Example 1 530 parts of diethylene glycol and 740 parts of phthalic anhydride were charged into a four-bottle flask equipped with a nitrogen inlet tube, a thermometer, a condenser for removing ester-formed water, and a stirring device.
React at 40°C to 160°C for 3 hours.
8KHOmy/q, water M base value 144 KOJI/ng
/9 (hereinafter, "medium" will be omitted) polyester polyol was obtained.

Synthesis Example 2 554 parts of polyester polyol obtained in Synthesis Example 1, 12
- 830 parts of hydroxystearin R, 7840 parts of ε-caprolactone, and 0.01 part of tetrabutyl titanate were charged into the same apparatus as in Synthesis Example 1, and reacted at 180°C for 7 hours to give an acid value of 24.2 and a hydroxyl value of 23.5. , a lactone polymer having a melting point of 46-47°C was obtained.

Synthesis Example 3 In the same apparatus as Synthesis Example 1, diethylene glycol 197
．． 2 parts, 275.3 parts of phthalic anhydride, 1102.5 parts of 12- and droxystearic acid, ε-kabu[]99528
8925 parts and 0.1 part of tetrabutyl titanate were added.
By reacting at 180°C for 7 hours, the acid value was 25.4.
, a lactone polymer having a melting point of 46-47 was obtained with 1 m of water (il 523.2).

Example 1 55 parts of unsaturated polyester resin obtained from maleic anhydride and 1,2-propylene glycol, 9245 stripes
parts, 50 parts of the resin obtained in Synthesis Example-2, 1 part of t-butyl perbenzoate, 3 parts of M2O, 120 parts of calcium carbonate,
After kneading 2 parts of carbon black as a pigment and 80 parts of glass fiber with a fiber length of 1 cm in a kneader, the mixture was aged at 40 DEG C. for one day to obtain a bulk molding compound.

This was injection molded at 150° C. and a pressure of 100 Kg/cIIi for 3 minutes to obtain a molded product with an even surface.

The molding shrinkage rate was 0.08 (%) of the expansion, the surface gloss was 60 degrees, the reflectance was 80-90%, and the hue was black.

Example 2 Unsaturated polyester resin 6 similar to that used in Example 1
0 parts, 40 parts of styrene, 14 parts in Synthesis Example-3, 30 parts of resin, 1 part of t-butyl perhenzoate, 100 parts of aluminum hydroxide, 1 part of Mg, 3 parts of zinc sudearyate, and 2 parts of carbon black. After kneading 80 parts of Gala 28M in a kneader, the mixture was aged at 40°C for one day to obtain a bulk molding compound.

When this was transfer-molded at 150° C. and a pressure of 100 kg/ci for 3 minutes, a molded product with an even surface was obtained.

The molding shrinkage rate was 0.08 (%) of the expansion.Good results were obtained with a surface gloss of 60 degrees reflection'$80-90%9 and a hue of black.

Claims (1)

[Scope of Claims] (1) a) 50 to 90% by weight of aliphatic oxycarboxylic acid b) 10 to 50% by weight of ester of polyhydric alcohol and aromatic polybasic acid or its anhydride a) and b) c) 90 to 60% by weight of ε-caprolactone, and a lactone polymer having an average molecular weight of 1,000 to 10,000. (2) A) 30 to 80 parts by weight of unsaturated polyester resin B) 70 to 20 parts by weight of ethylenically unsaturated monomer C) a) 50 to 90 parts by weight of aliphatic oxycarboxylic acid b) Polyhydric alcohol and aroma 10 to 50% by weight of an ester with a group polybasic acid or its anhydride, a total of 10 to 40% of a) and b), and c) 90 to 60% of ε-caprolactone, and has an average molecular weight of 1000 to 10000. 5 to 200 parts by weight of a low shrinkage agent made of a lactone polymer D) 40 to 400 parts by weight of an inorganic filler E) 10 to 200 parts by weight of a reinforcing agent F) 0.01 to 5 parts by weight of a polymerization initiator A low shrinkage thermosetting resin composition.