JPH02142814A - Reinforced resin composition - Google Patents

Abstract

PURPOSE:To improve the mechanical strengths at low cost by mixing specific cellulose and lingnocellulose reinforcing materials with a resin composition comprising an unsaturated polyester, a three-dimensional crosslinking reinforcing agent and a high-temperature initiation type polymerization initiator. CONSTITUTION:Cellulose and lignocellulose reinforcing materials (A) are mixed with an unsaturated polyester and a three-dimensional crosslinking reinforcing agent for the unsaturated polyester (e.g., diallyl phthalate oligomer) and a high- temperature initiation type polymerization initiator (e.g., dicumyl peroxide) to produce a reinforced resin composition. As the component (A), woodmeal, wood pulp, etc., can be used, and it is preferred that it is blended after an appropriate amount of unsaturated group is introduced into it by subjecting only the surface slightly to chemical modification, for example, by ethyrification with allyl glycidyl ether, thereby improving the interfacial adhesion strength with respect to the unsaturated polyester.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to reinforced resin compositions with improved mechanical strength, etc., and more specifically to cellulosic and lignocellulose into which (Δ) unsaturated groups have been introduced. The present invention relates to a reinforced resin composition with improved physical properties, comprising a reinforcing material, (1) an unsaturated polyester, (C) a 13-dimensional crosslinking reinforcing agent of an unsaturated polyester, and (D) a high-temperature polymerization initiator.

[Prior art]

There is a desire to develop more effective ways to use reproducible forest resources, and there is an urgent need to establish ways to use wood waste more effectively in industries that use wood as raw materials, such as the pulp industry and lumber industry. . One method is to use synthetic polymers as fillers, which have been conventionally used in combination with thermosetting t'l or thermosetting resins. When looking only at thermosetting resins, phenolic resins,
As a filler for diallyl phthalate resin, wood flour or the like is sometimes added at a high filling rate of 60% by weight to improve the appearance and physical properties of the resulting molded product.

From the perspective of effective use of wood, it is necessary to further increase the types of synthetic polymers that can be combined with wood, and to create more wood-synthetic polymer waste material systems. However, when chemically untreated wood flour or wood pulp is used as a filler in synthetic polymers,
In many cases, the mechanical strength of synthetic polymer molded articles is significantly lowered, and there is a limit to the extent to which it can be carried out industrially.

[Problems to be solved by the invention] The present invention takes the utilization of wood H one step further by rationally combining it with vesicles (・11 polynis wool).
By improving the problems in conventional technology, we have improved the production of wood flour, wood pulp,
and cellulosic or lignocellulosic materials such as seed hair fibers (hereinafter also referred to as cellulose-reinforced material A) 6
．． Adding two chemical modifications and blending it into unsaturated polyvarnish wool.
(On the contrary, it is more effective without reducing the mechanical strength.)
The present invention provides a novel reinforced resin composition having superior physical properties.

[Failure to solve the problem]

The inventors of the present invention have made extensive studies to solve the above problems, and have found that by chemically modifying only the surfaces of wood flour and wood pulp without reducing their cohesive strength, reactive unsaturated groups can be added. By introducing this, when used as a filler for unsaturated polyester resin, the interfacial adhesion between the cellulose reinforcing material and the unsaturated polyester matrix resin is improved in the cured molded product of (a), and the reinforcing effect is significantly improved. This discovery led to the present invention.

That is, the present invention chemically modifies only the surface as much as possible by very slight allylation or etherification with allyl glycidyl ether methacrylate, and makes unsaturated wood flour or wood pulp with By adding and blending polyester, its curing agent, and polymerization initiator, the cohesive force inherent in cellulosic reinforcing materials can be reduced after molding and curing at the necessary high temperatures and pressures. The interfacial adhesion strength with the unsaturated polyester cured resin matrix has been modified, resulting in a composition with better mechanical strength than a single cured resin molded product of unsaturated polyester and its curing agent. It is based on

As mentioned above, the cellulose-based reinforcing material used in the resin composition of the present invention is a cellulose-based or lignocellulose-based material, and specifically, it is a desolping pulp, a chemical pulp, or a semi-cellulosic material. In addition to wood pulp such as chemical pulp and mechanical pulp (thermomechanical pulp, Refined Crown 1 pulp, groundwood pulp, etc.),
Examples include seed wool fibers such as wood flour and cotton, and wood pulp is preferably used.

Moreover, the resin A. of the present invention. The unsaturated polyester resin used in the +1 product is a polyester mainly composed of unsaturated dibasic acids and dihydric alcohols, as well as vinyl monomers and diallyl phthalate oligomer resins, which are oligomerized and non-volatile. It is a thermosetting resin obtained by copolymerization with

Among these, unsaturated polyesters are made by condensing cyclophonic acids with double bonds in the molecule, such as maleic acid (or its anhydride) or fumaric acid, with dihydric alcohols such as ethylene glycol and propylene glycol. It is made of linear polyester. This product is soluble and fusible, but it has heavy bonds, so if you mix a vinyl monomer such as styrene or a sialyl phtacy 1 oligomer as a crosslinking agent, add a radical polymerization initiator, and heat it. , an insoluble and infusible thermosetting resin is j'7.

In addition to the radical polymerization initiator, a high-temperature initiator is used in the present invention;
Those that have a suitable temperature range for use include cumene hydroperoxide, tertiary sotylhydroperoxide, dicumyl peroxide, diterb to f-ruperoxide, etc.

As described above, the cellulose-based reinforcing material used in the present invention can be unsaturated by allylation, etherification with allyl glycidyl ether, etherification with glycidyl methacrylate, esterification with maleic anhydride, etc. It is something that is based on the basics. In this case, excessive chemical modification is undesirable because it deteriorates the inherent cohesiveness of the cellulosic reinforcing material and reduces its strength. Chemical modification within a range that does not impair the strength of cellulose-based reinforced materials,
Chemical modification limited to the surface portion is desirable and leads to improved physical properties of the reinforced resin composition. The desirable amount of double bond introduced is 2 to 35 in terms of iodine value (g. iodine/100 tX sample)
It is.

Next, although the proportion of each component constituting the resin 311 composition of the present invention is not limited to 'IM', cell 1-V
-The content of the abrasive reinforcement material θ in the J1 composition is 70%.
If it exceeds 7031., the mechanical strength of the resulting composition decreases. Is it possible to make it less than i amount%? ,! 1: □Yes. ■1, Person 2, The character ratio of vinyl monomers such as styrene and sialyl sotale-1/A ribomers used as cross-linking agents for unsaturated polyesters depends on the amount of unsaturated groups in the unsaturated polyesters, and is usually used. Use that 1'lL.

When producing the resin composition of the present invention, there are no particular restrictions on the order and method of blending each component, and each component is usually kneaded in a bi-ter, Banbury mixer 1 extruder, etc. It is done in this way.

Furthermore, various additives such as flame retardants, stabilizers, ultraviolet absorbers, plasticizers, lubricants, facial dyes, and other components can be appropriately blended into the resin composition of the present invention, if desired.

〔Example〕

The present invention will be explained in more detail with reference to production examples and examples below, but the embodiments of the present invention are not limited to these examples.

Manufacturing! ! ! LL (Manufacture of allylated main flour by Arcel method) 180 g of 40% caustic soda aqueous solution was added to 50 g of wood flour, and after stirring at room temperature for several minutes, 312 t of allyl bromide was added,
The reaction was carried out in an autoclave at 80° C. for 30 minutes to 31 minutes. Thereafter, it was washed alternately with methanol and deionized water until the washing solution became neutral, and dried <+2.

'JJ thick ((Manufacture of allylated thermomechanical pulp by solvent method) 60 ts of dried thermomechanical pulp, 21
Weigh out 135 toluene into a separable flask.
0ml and 40% aqueous sodium hydroxide solution were added, stirred, and M mercerized at room temperature for 1 hour. Then, allyl bromide 153
．． 6 g was added, the temperature was raised to 80°C, and the reaction was carried out for 30 minutes to 3 hours. Thereafter, it was washed and dried in the same manner as in Production Example 1.

1m9113 manufactured by Glycidyl Etherifier (Etherification of Momechanical Parb with glycidyl ether) Weighed 25 g of dried Lemomechanical Parb into a 21-volume separable flask, and added isopropanol 7.
Add 50ml and 53.5g of 14% caustic soda aqueous solution,
Stir for 1 hour at room temperature. Next, 200 ml of allyl glyconol ether, chrycidyl methacrylate 1, or n-butyl glycidyl ether for use in a control experiment was added, and the temperature was raised to 80°C, followed by reaction for 1 to 3 hours.

After the reaction was completed, the mixture was neutralized and washed with an aqueous acetic acid solution and methanol, and then dried.

M4 (+114 (Esterification of wood flour with maleic anhydride) 60 g of dry wood flour and 60 g of maleic anhydride were weighed into a 1 L separable flask, and reacted at 120°C with stirring for 15 minutes to 2 hours. After the reaction, unreacted maleic anhydride was Soxhlet-extracted using acetic acid for 8 hours, and then dried.

-Tall Shoik 1j-5- (Production of unsaturated polyester) 5
Put a stirring bar, a thermometer, an inert gas blowing tube, and a cooling tube into a 00 ml four L1 flask, weigh out 78 g of maleic anhydride, 167 g of propylene glycol, and add nitrogen gas. The mixture was stirred under an atmosphere and gradually heated using a mantle heater. It took about 1 hour to bring the temperature to 150-160℃, and then to 210℃ for 3 hours.
The reaction was allowed to proceed until the acid value reached 50 + iiJ.

``Tamanhua'' - Vacuum-dried allylated nermomechanical pulp with an iodine value of 31.4 and unsaturated polyester with an acid value of 50 prepared according to Production Example 5 were taken at various blending ratios, and the total amount of 30% by weight was taken. % amount of diallyl phthalate resin (however, a mixture of di7lyl phthalate-1 and 1,000 diallyl phthalate oligomers = = 3:7 (by weight) was used),
And tertiary butyl perbenzoate (TBP) in an amount of 1% by weight based on the total amount was weighed out so that the total amount was 25g, and heated and kneaded in a kneader (Toyo Seiki Uhoplast Mill) (temperature 60 ° C. , rotation speed] orpm, and kneaded for 10 minutes at a rotation speed of 5 orpm). The mixing amount other than the blending ratio of allylated thermomechanical pulp (abbreviated as allylated 1" M P) and unsaturated polyester and the mixed fibers were determined in advance as the optimum conditions through experiments. Each of the kneaded products was hot-press molded in a spacer frame with a diameter of 0.4 cm, which was sandwiched between two sheets of polyethylene terephthalate and a tosaw 1, and a film-like specimen was formed. First, pre-pressing was performed for 3 minutes at a hot rod temperature of 90°C and a pressure of 50 kg f/ct, followed by a hot rod temperature of 160°C and a pressure of 50 kg f/c.
The film was cured under heat and pressure for 6 minutes at a temperature of 50° C. to obtain a fill-like condition.

A rectangular specimen of 80 x 5 x 0.4 mm was cut out from the obtained sample film 1 and subjected to a tensile test. The tensile test was performed at a temperature of 20°C and a relative reading of GOR11.
-Conducted using Graph DC3-500 model. The experimental results are shown in FIGS. 1 to 3. The figure shows that tensile strength (σ) and fracture elongation rate (ε) largely depend on the mixing ratio of allylated Kizuki and unsaturated polyester, and are higher than the physical property values of unsaturated polyester alone, which are indicated by dotted lines in the figure. It is known that it can take on values. In particular, a sample with a mixing ratio of allylated TMP and unsaturated polycoastyl of 515 to 6/4 has high strength and at the same time high elongation at break. Iodination 31.4 and allylated 'rM+1 with a fairly high degree of substitution are used, and its dissolution progresses when kneaded with unsaturated polyester, and allylated TMP does not exist as a filler in the molded product. However, this is also confirmed by the behavior of Young's modulus (E) in Figure 3.

Point base I Iodine value 12.5 ~ produced by changing the reaction time in Production Example 2
31.4 vacuum-dried allylated TMP and unsaturated polyester with an acid value of 40 prepared according to Production Example 5 were taken in equal weights, and 30% by weight of diallyl phthalate resin (however, diallyl Phthalate monomer:
A mixture of diallyl phthalate oligomer = 3:1 (weight)) and sec-butyl perbenzoate (TBP) in an amount of 1% by weight based on the total amount were weighed out to a total of 25 g, and the same as in Example 1 was prepared. The mixture was kneaded and molded to obtain a film-like specimen, and its tensile strength properties were evaluated. The obtained results are shown in FIGS. 4 to 6.

In this case, the reaction with an allylation time of 0.51 and 3 hours, shown on the horizontal axis, results in an iodine value of 12.5252 and a reaction time of 3 hours.
1.4 allylated TMPs are obtained, respectively. No treatment (
When a zamomechanical pulp with an allylation time of 0 minutes is combined with an unsaturated polyester, both the tensile strength (σ) and the elongation at break (ε) are lower than those of the unsaturated polyester alone. Composites with unsaturated polyesters subjected to an allylation reaction time of 30 minutes (iodine value 12.5) showed higher values than unsaturated polyesters alone, as well as composites with untreated thermomechanical pulp.
It is a material with irregular physical properties. However, when the allylation is further advanced, the strength and fracture elongation rate of the resulting composite decrease again. This is thought to be because the cohesive force of the thermomechanical pulp fiber itself decreases as allylation progresses, and this is also supported by the relationship between Young's modulus (E) and allylation time (FIG. 6). From the above, in order to obtain molded composite materials with irregular physical properties, it is effective to introduce a small amount of unsaturated groups into thermomechanical pulp that can chemically react with unsaturated polyester during curing, but many It can be concluded that the introduction of No. 11 (introducing cellulose-based filler) causes a decrease in the physical properties of Material A, and is actually harmful.

Film-like specimens were prepared in the same manner as in Example 2, except that etherification with allyl glycidyl ether (abbreviated as AGP) prepared by changing the reaction time according to Production Example 3 was used. .

The results obtained are shown in FIGS. 7 to 9. In this case, the reactions with etherification times of 1.2 and 3 hours, shown on the horizontal axis, resulted in iodine values of 3.78.6°10 and 8.8°, respectively.
96 AGPs are obtained. It can be said that almost the same results as in Example 2 were obtained. That is, when the relationship between the iodine number, which indicates the amount of unsaturated groups introduced into thermomechanical pulp, and the tensile strength is shown together with the case of allylated TMI) in Example 2, Figure 1O is obtained. The optimum value is found around 10. These results also indicate that introducing unsaturated groups into cellulosic reinforcement improves the adhesion at the interface between it and the matrix and improves tensile properties. It is presumed that reducing the cohesiveness of the fibers and excessively increasing the adhesion at the interface causes stress concentration on the fibers, leading to a decrease in strength.

A film specimen was prepared in the same manner as in Example 2, except that a glycidyl methacrylate etherification thermomechanical valve (abbreviated as GMP) prepared according to Production Example 3 with different reaction times was used.

The obtained results are shown in FIGS. 11 to 13.

Curves with maximum values for both tensile strength (σ) and fracture elongation rate (ε) were obtained around 1 hour of etherification time, and it can be said that almost the same results as Example 2 were obtained.

Oane - Example y A film specimen was prepared in the same manner as in Example 2, except that maleic anhydride esterified wood flour prepared according to Packaging Example 4 with different reaction times was used. When its tensile properties were measured, a plot of the relationship between tensile strength and weight increase rate due to male/inner treatment showed a curve with a maximum around 2% weight increase rate, which was almost the same as in Example 2. The results were obtained.

n-butyl glycidyl ether etherified thermomechanical pulp (
A film specimen was prepared in the same manner as in Example 2, except that BGP (abbreviated as BGP) was used.

Note that this etherification does not introduce unsaturated groups into the wood fibers. In this sense, the data are those of the control experiment, and the results are shown in FIGS. 14 to 16.

First, all measured values for tensile strength (σ) and elongation at break (ε) are lower than those for molded products made of unsaturated polyester resin alone (no effect of substituent introduction is observed. It is natural that a chemical bond would not occur between the butyl group and the unsaturated polyester and the diallyl fukray resin, and that it would be impossible to improve the adhesion at the interface between the cellulose reinforcing material and the matrix resin. Looking at the elastic modulus (E), it can be said that as the reaction progresses, its value decreases, indicating that the cohesive strength of the filler decreases.

[Effects of the Invention] As detailed above, the resin composition of the present invention introduces a small amount of unsaturated groups into the cellulose-based reinforcing material, mainly on the surface thereof, within a range that does not reduce the mechanical strength etc. to tN. By doing so, when compounding with unsaturated polyester resin, the adhesive strength at the interface between the two increases, and the mechanical strength of the resulting resin composition is significantly improved compared to the case of unsaturated polyester resin alone. It has excellent characteristics and greatly contributes to cost reduction and improvement of physical properties of unsaturated polyester resins, and its industrial significance is extremely large.

[Brief explanation of the drawing]

Figures 1 to 3 show the tensile strength (by ratio) of allylated TMP and unsaturated polyester resin (UP), respectively.
σ), elongation at break (ε), and modulus of elasticity (E). Figures 4 to 6 show the changes in tensile strength (σ), elongation at break (ε), and modulus of elasticity (E), respectively, depending on the allylation time. It is a line diagram showing a change in E). Figures 7 to 9 show 8GP- etherified with allyl glycidyl ether, respectively.
It is a diagram showing changes in tensile strength (σ), fracture elongation rate (ε), and elastic modulus (E) depending on the etherification time of UP. This is a graph showing. Figures 11 to 13 show the tensile strength (σ) of MGP-LJP etherified with glycidyl methacrylate as a function of etherification time.
, is a diagram showing changes in fracture elongation rate (ε) and elastic modulus (E), and FIGS. 14 to 16 are graphs of BGP-LI I) etherified with n-butyl glycidyl ether.
Tensile strength (σ), fracture elongation rate (
ε) and a diagram showing changes in elastic modulus (E). (J2 row) and ot/H (%)3 (%)3 (Fri/Jha)D (%)3 (Fri/j No. ゛1)p (F-'/Jha)Ω (IP /J2) I), OI/M CFj/J glue) Ω (lL7#3jw), o I/H (F3/J'M) D (p, y, #ha), 01/go (F'/J glue) and 01/go(%)3 (%)3 (lL+/Jha)Ω

Claims (1)

[Claims] 1. (A) a cellulose-based and lignocellulosic reinforcing material, (B) an unsaturated polyester, (C) a three-dimensional crosslinking reinforcing agent for the unsaturated polyester, and (D) a high-temperature polymerization initiator. A reinforced resin composition. 2. The reinforced resin composition according to claim 1, wherein the cellulosic and lignocellulosic reinforcing materials are chemically modified to have an appropriate amount of unsaturated groups introduced therein.