JP2012040787A - Composite laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite laminated body comprising a foamed particle molding excelling in solvent resistance and excelling in adhesiveness to a thermosetting resin, and a thermosetting resin layer.SOLUTION: This composite laminated body comprises a polylactic acid-based resin formed particle molding, and a thermosetting resin layer stuck and laminated on a surface of the formed particle molding.

Description

  The present invention relates to a composite laminate, and more particularly to a composite laminate comprising a polylactic acid-based resin expanded particle molded body and a thermosetting resin layer.

  Conventionally known is a composite laminate in which a thermosetting resin layer is bonded to the surface of a synthetic resin foam and laminated. In particular, fiber reinforced plastics (FRP) containing fibers in the thermosetting resin layer are excellent in strength, lightness, and durability. Therefore, bathtubs, water tanks, temporary toilets, chairs, waterproof pans, vehicle panels, vehicle bodies It has been suitably used for ship bodies, floats, surfboards, snowboards, helmets, and the like.

However, since FRP generates heat during its curing reaction, it has a problem that the thick part is altered by its own reaction heat. Therefore, there is a limit to the improvement of mechanical properties such as bending strength by increasing the thickness of the composite laminate, and there is a limit to the shape that can be obtained, such as an increase in weight.
In order to obtain a thick-walled FRP while avoiding this, resin foams such as urethane foam and polyvinyl chloride foam were used as the FRP core material. However, since these are plate-shaped molded products, there is a restriction on the product shape, such as the need to perform machining according to the product shape.

  On the other hand, there is a polystyrene foam particle molded body as a synthetic resin foam having excellent formability. However, since this has a problem that it is dissolved by the monomer of the thermosetting resin, it is necessary to coat the surface with a solvent-resistant resin in advance, and further, it is used to avoid melting due to the heat of curing. There are limitations on possible thermosetting resins and curing conditions.

  Moreover, there is a polypropylene expanded particle molded body made of polypropylene as a synthetic resin particle expanded particle molded body having excellent heat resistance. However, this has the problem that the adhesiveness with a thermosetting resin is bad. In order to solve this problem, the present inventor has proposed blending maleic anhydride-modified polyolefin with polypropylene resin (Patent Document 1). However, this has a problem that it adheres to the mold during molding and impairs productivity.

  In order to solve this problem, the present inventor has proposed a foamed particle molded body obtained by in-mold molding foamed particles in which a styrene-diene copolymer is blended with a polyolefin resin (Patent Document 2). However, since this has poor adhesion to the thermosetting resin on the surface of the molded body, in order to obtain sufficient adhesive strength, the surface of the molded body must be cut to expose the cell cross section. ing.

  In order to solve this problem, the present inventor has developed foamed particles comprising expanded particles in which the ratio of the styrene-diene copolymer in the surface layer portion of the foamed particles comprising a blend of polyolefin resin and styrene-diene copolymer is increased. A compact was proposed (Patent Document 3) and succeeded in improving the adhesiveness with the thermosetting resin without cutting the surface of the compact. However, this molded body requires a crosslinking step in order to withstand the solubility due to the thermosetting resin monomer, and to prevent foaming during foaming due to lack of compatibility between the constituent materials. There is a problem that the process time during the production of particles becomes long.

JP 7-258450 A JP-A-9-59417 Japanese Patent Laid-Open No. 10-273551

  The present invention solves the above-mentioned conventional problems, and provides a composite laminate comprising a foamed particle molded body and a thermosetting resin layer, which are excellent in solvent resistance and adhesiveness with a thermosetting resin. That is the subject.

According to the present invention, the following composite laminate is provided.
[1]
A composite laminate comprising a polylactic acid-based resin expanded particle molded body and a thermosetting resin layer adhered and laminated on the surface of the expanded particle molded body.
[2]
The polylactic acid-based resin foamed particle molded body has an endothermic amount (Bfm) of the foamed particle molded body obtained under the following condition 1 based on the heat flux differential scanning calorimetry described in JIS K7122 (1987). : Endo) [J / g] and calorific value (Bfm: exo) [J / g] satisfy the following formula (1): The composite laminate according to 1 above.
70> [(Bfm: endo)-(Bfm: exo)]> 25 (1)
Condition 1
[Measurement of endotherm and calorific value]
The measured values of the endothermic amount (Bfm: endo) and the calorific value (Bfm: exo) were obtained by measuring 1 to 4 mg of a measurement sample collected from the foamed particle molded body as described in JIS K7122 (1987). In accordance with the measurement method, the value is determined based on the DSC curve obtained when heating and melting from 23 ° C. to 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min.
[3]
The polylactic acid-based resin expanded particles constituting the polylactic acid-based resin expanded particle molded body are obtained under the following condition 2 in accordance with the heat flux differential scanning calorimetry described in JIS K7122 (1987). The endothermic amount of the entire expanded particle (Br: endo) [J / g], the endothermic amount of the expanded particle surface layer (Brs: endo) [J / g], and the endothermic amount of the center of the expanded particle (Brc: endo) [ J / g] satisfies the following formulas (2) and (3): The composite laminate according to 1 or 2 above.
(Br: endo)> 25 (2)
(Brc: endo)> (Brs: endo) ≧ 0 (3)
Condition 2
[Measurement sample adjustment]
(Sample for measuring the endothermic amount of the foam particle surface)
The surface layer portion including the surface of the expanded particles is cut to collect the surface layer portion to obtain a measurement sample. In the cutting process, a measurement sample having a weight of 1/6 to 1/4 of the weight of the expanded particles before the cutting process is collected from the entire surface of one expanded particle.

(Sample for measuring endotherm at the center of expanded particles)
The entire surface of the foamed particles is removed by cutting, and the remainder of the foamed particles having a weight of 1/5 to 1/3 of the weight of the foamed particles before the cutting treatment is taken as a measurement sample.

[Measurement of endotherm]
The measured value of each endothermic amount, (Br: endo), (Brs: endo), or (Brc: endo) is measured with the polylactic acid resin expanded particles, the measurement sample collected from the surface layer of the expanded particles, or the expanded In accordance with the heat flux differential scanning calorimetry described in JIS K7122 (1987), 1 to 4 mg of a measurement sample collected from the center of the particle is heated and melted to a temperature 30 ° C. higher than the melting peak end temperature. After maintaining at that temperature for 10 minutes, cooling to 110 ° C. at a cooling rate of 2 ° C./min, holding at that temperature for 120 minutes, and then cooling to 40 ° C. at a cooling rate of 2 ° C./min. And a value obtained on the basis of a DSC curve obtained when heating and melting to a temperature 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min.
[4]
The polylactic acid-based resin expanded particles forming the polylactic acid-based resin expanded particle molded body are composed of a core layer composed of a polylactic acid-based resin, and a polylactic acid-based resin located on the surface side of the core layer. The difference between the softening point (A) [° C.] of the polylactic acid resin constituting the core layer and the softening point (B) [° C.] of the polylactic acid resin constituting the outer layer [(A )-(B)] exceeds 0 ° C. and is equal to or lower than 105 ° C. 4. The composite laminate according to any one of 1 to 3 above.
[5]
5. The composite laminate according to any one of 1 to 4, wherein the thermosetting resin layer contains a fiber substance.
[6]
6. The composite laminate according to any one of 1 to 5, wherein the thermosetting resin constituting the thermosetting resin layer is an unsaturated polyester resin.

  In the composite laminate of the present invention, the foamed particle molded body constituting the composite laminate is excellent in fusibility between foam particles, excellent in mechanical properties, excellent in solvent resistance, and thermosetting. It is an excellent reinforced plastic composite that is excellent in adhesiveness with resin and shape retention during thermosetting resin adhesive lamination and excellent in appearance, lightness, mechanical strength, durability, and heat resistance in the composite laminate.

FIG. 1 is an example of a DSC curve showing the endothermic amount (Br: endo) of a measurement sample obtained by a heat flux differential scanning calorimeter. FIG. 2 is an example of a DSC curve showing the endothermic amount (Br: endo) of a measurement sample obtained by a heat flux differential scanning calorimeter. FIG. 3 is an example of a DSC curve showing a calorific value (Bfc: exo) and an endothermic amount (Bfc: endo) of a measurement sample obtained by a heat flux differential scanning calorimeter. FIG. 4 is an example of a DSC curve showing a calorific value (Bfc: exo) and an endothermic amount (Bfc: endo) of a measurement sample obtained by a heat flux differential scanning calorimeter. FIG. 5 is an example of a DSC curve showing a calorific value (Bfc: exo) and an endothermic amount (Bfc: endo) of a measurement sample obtained by a heat flux differential scanning calorimeter.

Hereinafter, the composite laminate of the present invention will be described in detail.
The composite laminate of the present invention (hereinafter also simply referred to as “composite”) is a foamed particle molded body using a polylactic acid resin as a base resin, and a thermosetting material bonded and laminated on the surface of the foamed particle molded body. It consists of a resin layer.

  The foamed particle molded body used in the composite of the present invention is obtained by in-mold molding of polylactic acid resin foamed particles having a polylactic acid resin as a base resin. The polylactic acid resin expanded particles used in the present invention will be described below.

  The polylactic acid-based resin constituting the polylactic acid-based resin expanded particles (hereinafter also simply referred to as “expanded particles”) used in the present invention is composed of polylactic acid or a mixture of polylactic acid and another resin. . In addition, it is preferable that this polylactic acid is a polymer which contains 50 mol% or more of component units derived from lactic acid. Examples of the polylactic acid include (a) a polymer of lactic acid, (b) a copolymer of lactic acid and another aliphatic hydroxycarboxylic acid, and (c) a lactic acid, an aliphatic polyhydric alcohol, and an aliphatic polycarboxylic acid. A copolymer, (d) a copolymer of lactic acid and an aliphatic polyhydric carboxylic acid, (e) a copolymer of lactic acid and an aliphatic polyhydric alcohol, (f) a mixture of any combination of these (a) to (e), etc. Is included. The polylactic acid also includes what are called stereocomplex polylactic acid and stereoblock polylactic acid. Specific examples of lactic acid include L-lactic acid, D-lactic acid, DL-lactic acid or their cyclic dimer L-lactide, D-lactide, DL-lactide or a mixture thereof.

  Examples of other aliphatic hydroxycarboxylic acids in the above (b) include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxyheptanoic acid and the like. Examples of the aliphatic polyhydric alcohol in (c) and (e) above include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, decamethylene. Examples include glycol, glycerin, trimethylolpropane, and pentaerythritol. Examples of the aliphatic polyvalent carboxylic acid in (c) and (d) above include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, succinic anhydride, adipic anhydride, trimesic acid, and propanetricarboxylic acid. , Pyromellitic acid, pyromellitic anhydride and the like.

  Specific examples of the method for producing polylactic acid used in the present invention include, for example, a method of direct dehydration polycondensation using lactic acid or a mixture of lactic acid and aliphatic hydroxycarboxylic acid as a raw material (for example, disclosed in US Pat. No. 5,310,865). Production method), ring-opening polymerization method for polymerizing cyclic dimer (lactide) of lactic acid (for example, production method disclosed in US Pat. No. 2,758,987), cyclic dimer of lactic acid and aliphatic hydroxycarboxylic acid For example, a ring-opening polymerization method in which lactide or glycolide and ε-caprolactone are polymerized in the presence of a catalyst (for example, a production method disclosed in US Pat. No. 4,057,537), lactic acid, aliphatic dihydric alcohol, and aliphatic dihydric acid. A method of directly dehydrating polycondensation of a mixture of basic acids (for example, the production method disclosed in US Pat. No. 5,428,126), lactic acid and aliphatic divalent A method of condensing alcohol, an aliphatic dibasic acid and a polymer in the presence of an organic solvent (for example, a production method disclosed in European Patent Publication No. 071880 A2), dehydration polycondensation of a lactic acid polymer in the presence of a catalyst In producing a polyester polymer by carrying out the reaction, there can be mentioned, for example, a method of performing solid phase polymerization in at least a part of the steps, but the production method is not particularly limited. In addition, a small amount of an aliphatic polyhydric alcohol such as glycerin, an aliphatic polybasic acid such as butanetetracarboxylic acid, a polyhydric alcohol such as a polysaccharide may be coexisted and copolymerized. The molecular weight may be increased by using a binder (polymer chain extender) such as a polyisocyanate compound. Further, it may be branched by a branching agent typified by a polyhydric aliphatic alcohol such as pentaerythlit.

  The polylactic acid used in the present invention is preferably blocked at the molecular chain end. Thereby, the hydrolysis in the production process of the polylactic acid-based resin expanded particles can be more reliably suppressed, and the polylactic acid-based resin expanded particles that can withstand in-mold molding can be easily obtained. Furthermore, the durability of the polylactic acid-based resin expanded particle molded body (hereinafter also simply referred to as expanded particle molded body) obtained by in-mold molding is improved.

As said terminal blocker, a carbodiimide compound, an oxazoline compound, an isocyanate compound, an epoxy compound etc. can be used, for example. Of these, carbodiimide compounds are preferred.
Specifically, aromatic monocarbodiimide such as bis (dipropylphenyl) carbodiimide (for example, Stabaxol 1-LF manufactured by Rhein Chemie), aromatic polycarbodiimide (for example, Stabaxol P manufactured by Rhein Chemie, Stabaxol P400 manufactured by Rhein Chemie) And aliphatic polycarbodiimides such as poly (4-4′-dicyclohexylmethanecarbodiimide) (for example, Carbodilite LA-1 manufactured by Nisshinbo Chemical Co., Ltd.).
These end-capping agents may be used alone or in combination of two or more.
Moreover, 0.1-5 weight part is preferable per 100 weight part of polylactic acids, and, as for content of terminal blocker, 0.5-3 weight part is more preferable.

  Thus, the polylactic acid used in the present invention is preferably a modified polylactic acid resin modified with one or more modifiers selected from a carbodiimide compound, an epoxy compound, and an isocyanate compound, More preferred is a modified polylactic acid modified with a carbodiimide compound.

  In addition, the base resin constituting the foamed particles used in the present invention can be mixed with other resins as described above within a range not impairing the object and effects of the present invention. In this case, since the constituents of the heat absorption amount and the heat generation amount to be described later vary when other resins are mixed, in the present invention when a mixed resin of polylactic acid and another resin is used as the base resin. Regarding the constituent requirements for the endothermic amount and calorific value, not the base resin made of a mixed resin, but only polylactic acid among the polylactic acid and other resins constituting the base resin is the endothermic amount in this specification. Or the calorific value component requirements. The mixed resin of polylactic acid and other resin preferably contains 50% by weight or more of polylactic acid, more preferably 70% by weight or more, and still more preferably 90% by weight or more.

  Examples of other resins that can be mixed with polylactic acid include polyethylene resins, polypropylene resins, polystyrene resins, polyester resins, and the like. Among them, biodegradable aliphatic compounds containing at least 35 mol% of aliphatic ester component units Polyester resins are preferred. Examples of the aliphatic polyester resin in this case include hydroxy acid polycondensates other than the polylactic acid resin, ring-opening polymerization products of lactones such as polycaprolactone, polybutylene succinate, polybutylene adipate, polybutylene succinate adipate , Polycondensates of aliphatic polyhydric alcohols such as poly (butylene adipate / terephthalate) and aliphatic polycarboxylic acids.

  Examples of additives that can be blended in the expanded particles used in the present invention include colorants, flame retardants, antistatic agents, weathering agents, and conductivity-imparting agents. In addition, it is not preferable to mix the additive at a high concentration when disposal or recycling is assumed.

In addition, when an additive is added to the base resin, the additive can be directly kneaded into the base resin. Usually, however, a master batch of the additive is prepared in consideration of dispersibility and the like. It is preferable to knead the material resin.
Although the said additive changes also with kinds of additive, normally it is preferable to set it as 0.001-20 weight part with respect to 100 weight part of base resin, and also 0.01-5 weight part.

  Next, the polylactic acid-based resin expanded particles used in the present invention have a polylactic acid-based resin as a base resin, the expanded particles have a specific endothermic amount (Br: endo), and the endothermic amount of the expanded particle surface layer. The fact that it is preferable to have a specific relationship between (Brs: endo) and the endothermic amount (Brc: endo) at the center of the expanded particle will be described in detail.

In the polylactic acid-based resin expanded particles used in the present invention, the endothermic amount (Br: endo) [J / g] of the expanded expanded particles after heat treatment, which is obtained under the following condition 2 by the heat flux differential scanning calorimetry, is as follows. It is preferable that the expression (2) is satisfied.
(Br: endo)> 25 (2)
In the above formula (2), (Br: endo) is more than 25 [J / g] when the heat treatment is carried out under the condition that the crystallization of the polylactic acid constituting the expanded particles is sufficiently advanced. This means that the amount of the crystal component of the expanded particles by lactic acid is large. That is, it means that a foamed particle molded body with an increased crystallinity can be obtained by increasing the crystallinity of the polylactic acid constituting the foamed particles by sufficient heat treatment. Accordingly, it can be expected that the heat resistance such as the mechanical strength and the compressive strength at high temperature of the finally obtained expanded foam molded body is improved. From such a viewpoint, (Br: endo) is preferably 30 J / g or more, and more preferably 35 J / g or more. Moreover, the upper limit of (Br: endo) is approximately 70 J / g, and further 60 J / g.

Further, in the expanded particles, the endothermic amount (Brs: endo) [J / g] of the surface layer of the expanded particles after heat treatment and the endothermic amount (Brc: endo) [J / g] of the center portion of the expanded particles after the heat treatment. It is preferable that the relationship satisfies the following expression (3).
(Brc: endo)> (Brs: endo) ≧ 0 (3)

The fact that the relationship of the above formula (3) is satisfied means that the surface layer of the foamed particles is formed when heat treatment is performed under the condition that the crystallization of the polylactic acid constituting the foamed particle surface layer and the foamed particle central portion is sufficiently advanced. This means that the amount of the polylactic acid crystal component is smaller than the amount of the polylactic acid crystal component constituting the center part of the expanded particles. This is because the polylactic acid in the central part of the expanded particle is increased in crystallinity by sufficient heat treatment, and mainly the crystallinity of the polylactic acid in the central part of the expanded particle is improved. ) Formula is satisfied, and the heat resistance and the like of the entire expanded particles can be improved. On the other hand, the polylactic acid in the surface layer portion of the expanded particle has a crystallinity level lower than that of the center portion of the expanded particle even by sufficient heat treatment, and thus has a low softening point on the surface of the expanded particle. Therefore, it means that the foamed particles can exhibit excellent fusing property in the heat fusing property between the foamed particles at the time of in-mold molding regardless of the heat history before and after the production of the foamed particles. From this viewpoint, in order to further improve the fusion property of the surface layer of the expanded particle, the endothermic amount (Brs: endo) of the surface layer of the expanded particle is preferably 35 J / g or less (including 0). Moreover, in order to improve the heat resistance and mechanical strength of the center part of the expanded particle, the endothermic amount (Brc: endo) of the center part of the expanded particle is preferably 30 J / g or more, and more preferably 35 J / g or more. Further, the upper limit of (Brc: endo) is approximately 70 J / g, and further 60 J / g.
Further, (Brc: endo) and (Brs: endo) preferably have a calorific value difference of 3 J / g or more, and further a calorific value difference of 4 J / g or more. In addition, within the range which satisfies the said (3) Formula, the polylactic acid which comprises a foamed particle surface layer part may be a mixed resin of amorphous polylactic acid or amorphous polylactic acid, and crystalline polylactic acid. Good.

  Further, it is preferable that the values of (Brc: endo) and (Brs: endo) are largely different from each other for reasons such as the above-mentioned fusing property, but actually, they are not so different. The reason for this is, for example, the case where the polylactic acid-based resin particles for obtaining foamed particles are adjusted by a core layer having a specific softening point difference described later and an outer layer positioned on the surface side with respect to the core layer. It is difficult to extract a portion consisting only of the outer layer as a surface layer of the expanded particles and measure (Brs: endo) from the relationship of cutting out the expanded sample from the expanded particles. Therefore, as an actual measurement sample of (Brs: endo), the surface layer of the expanded particle including the outer layer including a part of the core layer is a measurement sample, and the value of (Brs: endo) is (Brc: endo) This is because it is close to the value of.

  In the present specification, the endothermic amount of the entire expanded particle (Br: endo) [J / g], the endothermic amount of the surface layer of the expanded particle (Brs: endo) [J / g], and the endothermic amount of the center of the expanded particle (Brc: endo) [J / g] is a measured value obtained under the following condition 2 in accordance with the heat flux differential scanning calorimetry described in JIS K7122 (1987).

Condition 2
[Measurement sample adjustment]
(Sample for measuring the endotherm of the entire expanded particle)
The foamed particles are basically used as a measurement sample without being cut.
(Sample for measuring the endothermic amount of the foam particle surface)
The surface layer portion including the surface of the expanded particles is cut to collect the surface layer portion to obtain a measurement sample. In the cutting treatment, a measurement sample having a weight of 1/6 to 1/4 of the weight of the foamed particles before the cutting treatment is collected from the entire surface of one foamed particle. Specifically, the surface layer portion may be cut using a cutter knife, a microtome, etc., and the surface layer portion may be collected and used for measurement. However, it should be noted that the entire surface layer portion of one foamed particle must be excised and the weight of the surface layer portion excised from one foamed particle is the weight of the foamed particle before cutting. It should be within the range of 1/6 to 1/4.
(Sample for measuring endotherm at the center of expanded particles)
The entire surface of the foamed particles is removed by cutting, and the remainder of the foamed particles having a weight of 1/5 to 1/3 of the weight of the foamed particles before the cutting treatment is taken as a measurement sample. Specifically, a cutting process may be performed with a cutter knife or the like for the purpose of cutting out an internal foam layer that does not include the surface of the foam particles, and the center of the foam particles may be used for measurement. However, it should be noted that the entire surface of one foamed particle must be excised, and 5 minutes of the weight of the foamed particle before cutting so as to have the same center as possible. The center part of the expanded particle is cut out within a range of 1 to 3 times. At this time, the cut out measurement sample is as similar as possible to the shape of the expanded particles before the cutting process.

[Measurement of endotherm]
The measured value of each endothermic amount, (Br: endo), (Brs: endo), or (Brc: endo) is measured with the polylactic acid resin expanded particles, the measurement sample collected from the surface layer of the expanded particles, or the expanded In accordance with the heat flux differential scanning calorimetry described in JIS K7122 (1987), 1 to 4 mg of a measurement sample collected from the center of the particle is heated and melted to a temperature 30 ° C. higher than the melting peak end temperature. After maintaining at that temperature for 10 minutes, cooling to 110 ° C. at a cooling rate of 2 ° C./min, holding at that temperature for 120 minutes, and then cooling to 40 ° C. at a cooling rate of 2 ° C./min. Based on a DSC curve (hereinafter also referred to as a second DSC curve) obtained when heating and melting to a temperature 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min. The value to be stored. When collecting the measurement sample of (Brs: endo) and (Brc: endo) when the measurement sample obtained from one foamed particle is less than 1 to 4 mg, the measurement sample collection operation is performed with a plurality of foam particles. It is necessary to adjust the measurement sample within the range of 1 to 4 mg. In addition, when collecting a sample of (Br: endo), if the weight of one foamed particle exceeds 4 mg, the foamed particle is divided into two equal parts and measured within the range of 1 to 4 mg. The sample needs to be adjusted.

  As shown in FIG. 1, the endothermic amount (Br: endo) is defined as point a where the endothermic peak is separated from the low-temperature side baseline of the second endothermic peak of the DSC curve, and the endothermic peak is the high-temperature side base. A point returning to the line is a point b, and is a value obtained from a straight line connecting the point a and the point b and the area of the portion indicating the endothermic amount surrounded by the DSC curve. In addition, the apparatus should be adjusted so that the baseline is as straight as possible. If the baseline is inevitably curved as shown in FIG. 2, the curved baseline on the low temperature side of the endothermic peak should be Perform drawing to maintain the curved state and extend to the high temperature side. Point a is the point where the endothermic peak is away from the curved low temperature side baseline, and the curved base line on the high temperature side of the endothermic peak is the curved state of the curve. A point where the endothermic peak returns to the curved high temperature side base line is plotted as point b. In addition, the endothermic amount (Brs: endo) and the endothermic amount (Brc: endo) are determined from the second DSC curve in the same manner as (Br: endo), and a straight line connecting the point a and the point b, and the DSC It is calculated | required from the area of the part which shows the endothermic amount enclosed by a curve.

  In the measurement of the endothermic amounts (Br: endo), (Brs: endo), (Brc: endo), the measurement condition of the DSC curve of the measurement sample is 120 ° C. holding for 120 minutes, 2 ° C./min. The reason for adopting the cooling rate and the heating rate of 2 ° C./min is that the endothermic amount (Br: endo), (Brs: endo), (Br): This is because the purpose is to obtain (Brc: endo).

  The values of the endothermic amounts (Br: endo), (Brs: endo), (Brc: endo) are the values obtained from the polylactic acid-based resin expanded particles used to obtain the expanded particle molded body, and the polylactic acid-based values. The value obtained from the expanded particles collected from the resin expanded particle molded body is the same value. That is, the values of the endothermic amounts (Br: endo), (Brs: endo), and (Brc: endo) do not vary depending on the thermal history of the expanded particles. Therefore, in the present invention, the endothermic amounts (Br: endo), (Brs: endo), and (Brc: endo) of the polylactic acid resin foamed particles constituting the polylactic acid resin foamed particle molded body are expressed as foamed particles. It can obtain | require by the conditions 2 mentioned above from the polylactic acid-type resin expanded particle used in order to obtain a molded object, or the expanded particle extract | collected from a polylactic acid-type resin expanded particle molded object.

  In the present invention, the polylactic acid-based resin foamed particles constituting the polylactic acid-based resin foamed particle molded body have a specific endothermic amount (Br: endo), so that the heat-treated foamed particles are molded in-mold, or A foamed particle molded body having excellent mechanical strength and compressive strength at a high temperature can be obtained by heat treatment of the foamed particle molded body after in-mold molding of the foamed particles. Further, the endothermic amount (Brs: endo) of the surface layer of the foamed particle is equal to the endothermic amount (Brc: endo) at the center of the foamed particle, even though the whole foamed particle satisfies the specific endothermic amount (Br: endo) condition. ) Is lower, the softening temperature of the surface of the foamed particles can be kept low regardless of the thermal history of the foamed particles, and the foamed particles have excellent fusion properties during in-mold molding.

Particularly, in the case of polylactic acid resin foamed particles used for in-mold molding, the endothermic amount (Bfc: endo) at the center of the foamed particles before heat treatment, which is obtained under the following condition 3 by the heat flux differential scanning calorimetry method: J / g] and the calorific value (Bfc: exo) [J / g] preferably satisfy the following formula (4).

40> [(Bfc: endo)-(Bfc: exo)]> 10 (4)

Condition 3
[Measurement sample adjustment]
(Measurement of endothermic and calorific value at the center of expanded particles)
The entire surface of the foamed particles is cut and removed in the same manner as in the method for preparing the endothermic measurement sample at the center of the foamed particles in Condition 2, and the weight is 1/5 to 1/3 of the weight of the foamed particles before cutting. The remainder of the expanded particles is collected as a measurement sample.
[Measurement of endotherm and calorific value]
The measured values of the endothermic amount (Bfc: endo) and the calorific value (Bfc: exo) were measured by 1 to 4 mg of a measurement sample collected from the center part of the expanded particles, and the heat flux differential scanning described in JIS K7122 (1987). In accordance with the calorimetric method, a DSC curve (hereinafter also referred to as the first DSC curve) obtained when heating and melting from 23 ° C. to 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min. ). In addition, when the measurement sample obtained from one expanded particle is less than 1-4 mg, it is necessary to adjust the measurement sample within the range of 1 to 4 mg by performing the measurement sample collection operation on a plurality of expanded particles. is there.

  The difference [(Bfc: endo) − (Bfc: exo)] in the above equation (4) is the difference between the crystallized portion already present in the center of the expanded particle and the measurement at the time of the heat flux differential scanning calorimetry. In the temperature rising process, the endothermic amount (Bfc: endo), which is the energy absorbed when the center part of the expanded particle crystallizes, and the center part of the expanded particle in the temperature rising process of differential scanning calorimetry of heat flux Represents the difference from the calorific value (Bfc: exo), which is the energy released by crystallization, and the smaller the difference, the less the crystallization of the foamed particle center before the heat flux differential scanning calorimetry. This means that the larger the difference is, the closer the value of the endothermic amount (Bfc: endo) is, the more the crystallization at the center of the expanded particles progressed before the measurement. The difference [(Bfc: endo) − (Bfc: exo)] has a wide secondary foaming property when foamed particles are molded in-mold and a molding temperature range in which a good foamed-particle molded body is obtained when molding in-mold. From the viewpoint, it is preferable to be within the above range. Further, from the viewpoint of secondary foaming properties, it is preferably 35 J / g or less, particularly 30 J / g or less.

  On the other hand, the difference [(Bfc: endo)-(Bfc: exo)] is further 15 J / g or more, particularly 20 J / g, from the viewpoints of easy temperature adjustment during molding and prevention of shrinkage of the in-mold foam molding. The above is preferable.

  In the expanded particles used in the present invention, the endothermic amount (Bfc: endo) is preferably 30 to 70 J / g. The larger the endothermic amount (Bfc: endo), the higher the crystallinity of the polylactic acid-based resin constituting the expanded particles due to heat treatment, and finally the expanded particle molded body is adjusted to have a high mechanical strength. I can do it. On the other hand, if the endothermic amount (Bfc: endo) is too small, the mechanical strength of the foamed particle molded body, particularly the mechanical strength at high temperatures, may be insufficient. From this viewpoint, (Bfc: endo) is more preferably 35 J / g or more. Moreover, the upper limit of (Bfc: endo) is approximately 70 J / g, and further 60 J / g.

  The calorific value (Bfc: exo) is 5 to 30 J / g, more preferably 10 to 10 in relation to the adjustment of the difference [(Bfc: endo) − (Bfc: exo)] and the endothermic amount (Bfc: endo). 25 J / g is preferable from the viewpoint of excellent secondary foamability and moldability of the foamed particles. The larger the calorific value (Bfc: exo), the more the crystallization of the center part of the expanded particles made of crystalline polylactic acid resin has not progressed before the heat flux differential scanning calorimetry.

In the present specification, the calorific value (Bfc: exo) and the endothermic amount (Bfc: endo) of the expanded particles are the heat flux differential scanning calorimetry described in JIS K7122 (1987) as described above (Condition 3). The calorific value (Bfc: exo) and the endothermic amount (Bfc: endo) are measured according to the following criteria.
The exothermic amount (Bfc: exo) of the expanded particles is defined as a point c where the exothermic peak departs from the low-temperature base line of the first DSC curve, and a point d where the exothermic peak returns to the high-temperature base line. As a value obtained from a straight line connecting the points c and d and the area of the portion showing the heat generation amount surrounded by the DSC curve. Further, the endothermic amount (Bfc: endo) of the expanded particles is defined as a point e where the endothermic peak departs from the low temperature side baseline of the first DSC curve, and the endothermic peak returns to the high temperature side baseline. Is a point f, and a value obtained from the area connecting the straight line connecting the point e and the point f and the endothermic amount surrounded by the DSC curve. However, the apparatus is adjusted so that the baseline in the first DSC curve is as straight as possible. If the baseline is inevitably curved, the curved baseline on the low temperature side of the exothermic peak is extended to the high temperature side while maintaining the curved state of the curve. The point at which the exothermic peak deviates from the point c, and the curved base line on the high temperature side of the exothermic peak is extended to the low temperature side while maintaining the curved state of the curve, and the exothermic peak appears on the curved high temperature side baseline Let the point to return be a point d. Further, the base line curved at the low temperature side of the endothermic peak is extended to the high temperature side while maintaining the curved state of the curve, and the point at which the endothermic peak moves away from the curved base line at the low temperature side is the endothermic point. Drawing is performed to extend the curved base line on the high temperature side of the peak to the low temperature side while maintaining the curved state of the curve, and the point where the endothermic peak returns to the curved high temperature side baseline is defined as a point f.

  For example, in the case shown in FIG. 3, the calorific value (Bfc: exo) of the foamed particles is obtained from the area of the portion showing the calorific value surrounded by the straight line connecting the points c and d defined as described above and the DSC curve. Then, the endothermic amount (Bfc: endo) of the expanded particles is obtained from the area of the portion indicating the endothermic amount surrounded by the straight line connecting the point e and the point f determined as described above and the DSC curve. In the case shown in FIG. 4, since it is difficult to determine the points d and e as described above, the intersection of the straight line connecting the points c and f determined as described above and the DSC curve. Is determined as a point d (point e), and the heat generation amount (Bfc: exo) and the heat absorption amount (Bfc: endo) of the expanded particles are obtained. Also, as shown in FIG. 5, when a small exothermic peak occurs on the low temperature side of the endothermic peak, the exothermic amount (Bfc: exo) of the expanded particles is the area of the first exothermic peak in FIG. It is obtained from the sum of A and the area B of the second exothermic peak. That is, the area A is defined as a point c where the exothermic peak moves away from the low temperature side baseline of the first exothermic peak, and a point d where the first exothermic peak returns to the high temperature side baseline. It is assumed that the area A of the portion showing the heat generation amount surrounded by the straight line connecting the point d and the DSC curve. The area B is defined as a point g where the second exothermic peak is separated from the low temperature side baseline of the second exothermic peak, a point f where the endothermic peak returns to the high temperature side baseline, and a point g. An intersection point between the line connecting the point f and the DSC curve is defined as a point e, and an area B indicating the amount of heat generated between the line connecting the point g and the point e and the DSC curve is shown. On the other hand, in FIG. 5, the endothermic amount (Bfc: endo) of the expanded particles is a value obtained from the area of the portion indicating the endothermic amount surrounded by the straight line connecting the points e and f and the DSC curve.

  In the measurement of the exothermic amount (Bfc: exo) and the endothermic amount (Bfc: endo), the reason why the heating rate of 2 ° C./min is adopted as the measurement condition of the DSC curve is that the exothermic peak and the endothermic peak are as much as possible. A heating rate of 2 ° C./min is preferred when separating and obtaining an accurate endothermic quantity (Bfc: endo) and [(Bfc: endo) − (Bfc: exo)] by heat flux differential scanning calorimetry. This is based on the knowledge of the inventors.

  The polylactic acid resin foamed particles satisfying the formulas (2), (3), and (4) are composed of, for example, a core layer composed of a polylactic acid resin and another polylactic acid resin. It can be obtained by producing expanded particles comprising an outer layer covering the core layer. However, in the foamed particles of the present invention, the outer layer does not need to cover the entire core layer, and as long as the foamed particles satisfy the expressions (2) and (3), the resin constituting the core layer is foamed. There may be a portion exposed on the particle surface.

The softening point (B) [° C.] of the polylactic acid resin constituting the outer layer is lower than the softening point (A) [° C.] of the polylactic acid resin constituting the core layer, and the softening point (A) And the softening point (B) [(A) − (B)] is preferably more than 0 ° C. and not more than 105 ° C., more preferably 15 to 105 ° C., and still more preferably 20 ~ 105 ° C. The foamed particles having the difference within the above range can be obtained by a method described later, such as a co-extrusion method of a polylactic acid resin showing softening points (B) and (A) constituting the outer layer and the core layer. Expanded particles that can efficiently obtain expanded particles satisfying the formulas (2), (3), and (4), and exhibit excellent heat-fusibility during in-mold molding. It becomes.
The softening point of the polylactic acid resin constituting the outer layer is the softening point of the polylactic acid resin constituting the core layer from the viewpoint of the handleability of the foamed particles and the mechanical strength at high temperatures of the obtained foamed particle molded body. Is within the above range, and is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and particularly preferably 65 ° C. or higher.

  The softening point in this specification means the Vicat softening temperature measured by the A50 method based on JIS K7206 (1999). As a measurement test piece, after the polylactic acid resin is sufficiently dried using a vacuum oven, it is pressurized under the conditions of 200 ° C. and 20 MPa, and an air venting operation is performed as necessary so that bubbles are not mixed. A test piece having a length of 20 mm × width of 20 mm × thickness of 4 mm is prepared, and the test piece is annealed in an oven at 80 ° C. for 24 hours and used for measurement. As a measuring apparatus, “HDT / VSPT test apparatus MODEL TM-4123” manufactured by Ueshima Seisakusho Co., Ltd. can be used.

In the foamed particles composed of a core layer and an outer layer that are preferably used in the present invention, the weight ratio of the resin forming the core layer to the resin forming the outer layer is 99.9: 0.1 to 80:20. More preferably, it is 99.7: 0.3-90: 10, More preferably, it is 99.5: 0.5-92: 8. If the weight ratio of the resin forming the outer layer of the expanded particles is too small, the thickness of the outer layer portion of the expanded particles is too thin and the effect of improving the fusing property at the time of molding of the expanded particles is reduced. It becomes easy for the melt | fusion of this to become inadequate. In addition, production problems may occur when the resin particles are produced. On the other hand, if the weight ratio of the resin forming the outer layer is too large, the resin forming the outer layer foams more than necessary, and the fusion property during molding of the foamed particles may be reduced. Furthermore, there is a possibility that the mechanical properties of the foamed particle molded body are likely to be lowered. It is not necessarily excluded that the resin forming the outer layer is foamed. Accordingly, since the weight ratio between the resin forming the core layer of the foamed particles and the resin forming the outer layer is within the above range, the fusion strength between the foamed particles is increased, so that the obtained foam is obtained. The particle compact has excellent mechanical properties, and the mechanical properties are further improved by increasing the proportion of the core layer that contributes to improving the physical properties of the expanded particles.
In addition, the adjustment of the weight ratio of the resin forming the core layer in the foamed particles and the resin forming the outer layer is performed by forming a core layer of polylactic acid-based resin particles (hereinafter also referred to as resin particles). This is done by adjusting the weight ratio of the resin forming the outer layer and the resin forming the outer layer.

  In the foamed particles used in the present invention, the end-blocking agent for the polylactic acid resin constituting the foamed particles is preferably added to at least the core layer, and is added to both the core layer and the outer layer. It is more preferable. Since the polylactic acid resin constituting at least the core layer, preferably both the core layer and the outer layer, is end-capped, hydrolysis during the production of the expanded particles of the resin can be suppressed, and the expanded particles can be stably produced. become able to. Furthermore, hydrolysis during production of the foamed particle molded body can be suppressed, leading to stable production of the foamed particle molded body, and improvement in durability can be expected when used as a composite laminate.

  As for the thickness of the outer layer of the expanded particles, it is preferable that the thickness is thinner because bubbles are less likely to be generated in the outer layer and the mechanical properties of the expanded expanded product are improved. In addition, when the outer layer is too thin, there is a concern about the effect of improving the fusibility between the expanded particles, but if the thickness is within the following range, the effect of improving the fusibility is sufficiently exhibited. That is, the average thickness of the outer layer of the expanded particles is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, and particularly preferably 0.3 to 5 μm. In order to adjust the average thickness of the outer layer of the expanded particles to be in the above range, the average thickness of the outer layer of the resin particles may be adjusted by adjusting the weight ratio of the outer layer and the core layer at the resin particle stage. The average thickness of the outer layer of the resin particles varies depending on the weight of the resin particles, the expansion ratio, etc., but is preferably 2 to 100 μm, more preferably 3 to 70 μm, and particularly preferably 5 to 50 μm.

  The average thickness of the outer layer of the expanded particles is measured as follows. The expanded particles are roughly divided into two equal parts, and the thickness of the outer layer at four locations on the upper, lower, left and right sides of the cross section is determined from the photograph of the enlarged cross section, and the average is defined as the thickness of the outer layer of one expanded particle. This operation is performed for 10 expanded particles, and the value obtained by arithmetically averaging the thicknesses of the outer layers of the expanded particles is taken as the average thickness of the outer layers of the expanded particles. The average thickness of the outer layer of resin particles is also measured by the same method. In addition, when the outer layer is partially formed around the core layer, the thickness of the four outer layers may not be measured by any means, but in that case, obtain the outer layer thickness of any four locations that can be measured, The average is defined as the thickness of the outer layer of one foamed particle or resin particle. Further, when it is difficult to understand the thickness of the outer layer of the expanded particles, the resin particles can be produced by adding a colorant to the resin constituting the outer layer in advance.

  The apparent density of the expanded particles used in the present invention is preferably 25 to 400 g / L, and preferably 40 to 200 g / L from the viewpoint of excellent lightness, in-mold moldability, and mechanical properties. More preferred. If the apparent density is too small, the shrinkage rate after in-mold molding may increase, and if the apparent density is too large, the apparent density will tend to vary widely, and the foamed particles at the time of heat molding in the mold This leads to variations in expansibility, fusibility, and apparent density, and there is a risk of deterioration in physical properties of the obtained foamed particle molded body.

The apparent density of the expanded particles in this specification is measured as follows.
The expanded particles are allowed to stand for 10 days in a temperature-controlled room under conditions of atmospheric pressure, relative humidity 50%, and 23 ° C. Next, the weight W1 (g) of the expanded particle group of about 500 ml left in the same constant temperature room for 10 days is measured, and the measured expanded particle group is water having a temperature of 23 ° C. using a tool such as a wire mesh. Sink into a measuring cylinder containing. Next, the volume V1 (L) of the expanded particle group read from the rise in the water level, after subtracting the volume of the tool such as a wire mesh, is measured, and the weight W1 of the expanded particle group placed in the measuring cylinder is divided by the volume V1 ( W1 / V1) to obtain the apparent density.

  Moreover, the average cell diameter of the polylactic acid-based resin expanded particles used in the present invention is preferably 30 to 500 μm from the viewpoint of further improving the in-mold moldability and the appearance of the obtained expanded foam molded body, and 50 More preferably, it is -250 micrometers.

The average cell diameter of the expanded particles is measured as follows.
Based on an enlarged photograph obtained by photographing a cut surface obtained by dividing the expanded particle into approximately equal parts by a microscope, it can be obtained as follows. In the enlarged photograph of the cut surface of the expanded particle, four line segments passing through the approximate center of the bubble cut surface are drawn from one surface of the expanded particle to the other surface. However, the line segments are drawn so as to form radial straight lines extending in eight directions at equal intervals from the approximate center of the bubble cut surface to the cut particle surface. Next, the total number N of bubbles that intersect the four line segments is determined. A total sum L (μm) of the lengths of the four line segments is obtained, and a value (L / N) obtained by dividing the total L by the total N is defined as an average cell diameter of one expanded particle. This operation is carried out for 10 expanded particles, and the value obtained by arithmetically averaging the average cell diameter of each expanded particle is taken as the average cell diameter of the expanded particles.

  Further, the closed cell ratio of the expanded particles used in the present invention is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. If the closed cell ratio is too small, the secondary foamability of the foamed particles tends to be inferior, and the mechanical properties of the resulting foamed particle molded body tend to be inferior. In the present invention, as the polylactic acid-based resin constituting the base resin of the expanded particles, at least the polylactic acid-based resin that constitutes the core layer has the molecular chain end blocked as described above. It is preferable for obtaining a high closed cell ratio.

The closed cell ratio of the expanded particles is measured as follows.
The expanded particles are allowed to stand for 10 days in a temperature-controlled room at atmospheric pressure, relative humidity of 50% and 23 ° C. Next, in the same constant temperature room, the apparent volume Va is accurately measured by the submersion method as follows using the foamed particles after curing having a bulk volume of about 20 cm ³ as a measurement sample. After the sample for measurement in which the apparent volume Va is measured is sufficiently dried, the measurement is performed by an air comparison type hydrometer 930 manufactured by Toshiba Beckman Co., Ltd. according to the procedure C described in ASTM-D2856-70. The true volume Vx of the working sample is measured. And based on these volumes Va and Vx, the closed cell rate is calculated by the following formula (5), and the average value of N = 5 is set as the closed cell rate of the expanded particles.

Closed cell ratio (%) = (Vx−W / ρ) × 100 / (Va−W / ρ) (5)
However,
Vx: the sum of the true volume of the expanded particles measured by the above method, that is, the volume of the resin constituting the expanded particles and the total volume of bubbles in the closed cell portion in the expanded particles (cm ³ )
Va: The apparent volume of the expanded particles (cm ³ ) measured from the rise in the water level after the expanded particles are submerged in a graduated cylinder containing water.
W: Weight of the foam particle measurement sample (g)
ρ: Density of resin constituting expanded particles (g / cm ³ )

  By performing in-mold molding using the expanded particles, a polylactic acid-based resin expanded particle molded body is obtained. The shape is not particularly limited, and a plate shape, a column shape, a container shape, and a block shape can be obtained as a three-dimensional complicated shape or a particularly thick one.

  The foamed particle molded body is particularly composed of the above-mentioned foamed particles, so that the heat-fusibility between the foamed particles is excellent, and the polylactic acid resin constituting the foamed particle molded body is heat-treated. As a result, a foamed particle molded article having excellent heat resistance such as rigidity, compressive strength at high temperature, and dimensional stability, and particularly excellent adhesion to a thermosetting resin is obtained.

Therefore, in the foamed particle molded body, the endothermic amount (Bfm: endo) [J / g] and the calorific value (Bfm) of the foamed particle molded body before heat treatment, which are determined by the heat flux differential scanning calorimetry method under the following condition 1 : Exo) [J / g] preferably satisfies the following formula (1).
70> [(Bfm: endo)-(Bfm: exo)]> 25 (1)

Condition 1
[Measurement of endotherm and calorific value]
The measured values of the endothermic amount (Bfm: endo) and the calorific value (Bfm: exo) were obtained by measuring 1 to 4 mg of a measurement sample collected from the foamed particle molded body as described in JIS K7122 (1987). In accordance with the measurement method, the value is determined based on the first DSC curve obtained when heating and melting from 23 ° C. to 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min.

  The difference [(Bfm: endo) − (Bfm: exo)] in the above formula (1) is the crystallization part that the foamed particle molded body already had when performing the heat flux differential scanning calorimetry, Endothermic amount (Bfm: endo), which is energy absorbed when the foamed particle molded body crystallizes in the temperature rising process, and in the temperature rising process of heat flux differential scanning calorimetry, This represents the difference from the calorific value (Bfm: exo), which is the energy released by crystallization. The smaller the difference, the less the crystallization of the foamed particle molded body before the heat flux differential scanning calorimetry. This means that the larger the difference is, the closer the value of the endothermic amount (Bfm: endo) is, the more the crystallization of the foamed particle molded body proceeds before the measurement. The difference [(Bfm: endo) − (Bfm: exo)] is that the polylactic acid resin constituting the foamed particle molded body is sufficiently crystallized by heat treatment, resulting in rigidity, compressive strength at high temperature, and dimensional stability. From the viewpoint of having excellent properties as a base material of the composite laminate, it is preferably within the above range, more preferably 30 to 70 J / g, and particularly preferably 35 to 60 J / g.

  In the foamed particle molded body used in the present invention, the endothermic amount (Bfm: endo) is preferably 30 to 70 J / g, more preferably 35 to 65 J / g. The larger the endothermic amount (Bfm: endo), the higher the mechanical strength of the expanded foam molded article can be adjusted. On the other hand, if the endothermic amount (Bfm: endo) is too small, the mechanical strength of the foamed particle molded body, particularly the mechanical strength at high temperatures, may be insufficient.

  Further, the calorific value (Bfm: exo) is 5 J / g or less (including 0) in relation to the adjustment of the difference [(Bfm: endo) − (Bfm: exo)] and the endothermic amount (Bfm: endo). Further, it is preferably 3 J / g or less (including 0). The larger the heating value (Bfm: exo), the more the crystallization of the foamed particle molded body made of the polylactic acid resin has not progressed before the heat flux differential scanning calorimetry.

  In the present specification, the value of the calorific value (Bfm: exo) and endothermic amount (Bfm: endo) of the expanded foam molded body is the same as that of the expanded particle except that a measurement sample collected from the expanded foam molded body is used. It is calculated | required based on the DSC curve of the 1st time obtained by the heat flux differential scanning calorimetry method similarly to calorific value (Bfc: exo) and endothermic quantity (Bfc: endo). In addition, the collection of the measurement sample from the expanded particle molded body for measuring the calorific value (Bfm: exo) and the endothermic amount (Bfm: endo) is performed by cutting out the expanded particles present on the surface portion of the expanded particle molded body. It will be done by.

  The bulk density of the foamed particle molded body constituting the composite laminate of the present invention obtained as described above is preferably 15 to 300 g / L from the viewpoint of being lightweight and excellent in mechanical properties, More preferably, it is 25-180 g / L.

  The closed cell ratio of the foamed particle molded body is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. If the closed cell ratio is too low, mechanical properties such as compression strength of the foamed particle molded body may be lowered.

  The measurement of the closed cell ratio of the foamed particle molded body was performed by cutting a sample of 25 × 25 × 30 mm from the center of the foamed particle molded body (cutting off all skin) and using it as a measurement sample. It can be obtained in the same manner as the measurement.

The foamed particle molded article is excellent in the fusion property between the foamed particles, and the fusion rate is preferably 50% or more, more preferably 60% or more, and particularly preferably 80% or more. A foamed particle molded body having a high fusion rate is excellent in mechanical properties, particularly bending strength.
The fusing rate means a material destruction rate based on the number of fractured surface foamed particles when the foamed particle molded body is ruptured. The unfused part does not break the material and peels at the interface of the foamed particles. To do.

Hereinafter, the manufacturing method of the polylactic acid-type resin expanded particle used by this invention is demonstrated.
Examples of the method for producing the expanded particles include an extrusion foaming method, a gas impregnation preliminary foaming method, a dispersion medium releasing foaming method, and other foaming methods based on these methods and principles.

  The extrusion foaming method includes, for example, melt-kneading a polylactic acid resin in an extruder, press-fitting a physical foaming agent into the extruder, and kneading to obtain a foamable molten resin. This is a method for producing expanded particles by cutting a strand-like foam obtained by extrusion. In this method, the resin particle production process, the foaming agent impregnation process, and the foaming process are performed as one process using one extruder. Regarding this method, refer to JP2007-100025A and International Publication WO2008 / 123367. When the foamed particles of the present invention are obtained by the extrusion foaming method, those satisfying the constituent requirements of the surface layer and the central portion of the foamed particles of the present invention can be obtained by the coextrusion foaming method.

  In the gas-impregnated pre-foaming method, for example, after melt-kneading a polylactic acid-based resin with an extruder, resin particles are produced by extruding and cutting into strands, and the resin particles are filled in a pressure-resistant sealed container, By injecting a physical foaming agent into the pressure vessel, the resin particles are impregnated with the foaming agent to produce foamable resin particles. The foamable resin particles are put into a pre-foaming machine, and steam, hot air, or their This is a method of obtaining foamed particles by foaming expandable resin particles by heating with a heating medium such as a mixture. In the production of the above resin particles, a strand cut method, an underwater cut method or the like can be appropriately selected. Further, in the step of impregnating the resin particles with the foaming agent by press-fitting a physical foaming agent into the pressure vessel, a liquid phase impregnation method or a gas phase impregnation method can be appropriately selected. In the gas impregnation pre-foaming method, the resin particle production process, the foaming agent impregnation process, and the foaming process are performed as separate processes. For this method, refer to JP 2000-136261 A, JP 2006-282750 A, and the like. When the expanded particles of the present invention are obtained by the gas-impregnated pre-expanded method, resin particles comprising an outer layer and a core layer are produced by a coextrusion molding method described later, and the surface layer and the central portion are constituted from the resin particles. Expanded particles satisfying the requirements can be obtained.

  The dispersion medium releasing foaming method is, for example, producing a resin particle by melt-kneading a polylactic acid resin with an extruder and then extruding it into a strand shape and cutting it, and the resin particle is placed in an aqueous medium in a closed container. The foamed resin particles are produced by impregnating with a physical foaming agent by dispersing and heating to form foamable resin particles, and releasing the foamable resin particles together with an aqueous medium from a closed container at a foaming suitable temperature. In this method, the resin particle production process, the foaming agent impregnation process, and the foaming process can be performed as separate processes. However, as described above, the foaming agent impregnation process and the foaming process are usually performed as one process. Hereinafter, the production method of the polylactic acid-based resin expanded particles will be described in detail with a focus on the dispersion medium release foaming method.

In the resin particle production process, the resin particles can be produced by a strand cut method, an underwater cut method, or the like in which additives necessary for the base resin are blended, extruded and pelletized. However, since it is preferable that the foamed particles used in the present invention satisfy the formulas (2) and (3), in that case, resin particles composed of a core layer and an outer layer may be produced.
The resin particles comprising the core layer and the outer layer are described in, for example, Japanese Patent Publication No. 41-16125, Japanese Patent Publication No. 43-23858, Japanese Patent Publication No. 44-29522, Japanese Patent Publication No. 60-185816, and the like. Further, it can be manufactured using a co-extrusion technique.

  In the coextrusion method, generally, an apparatus in which a core layer forming extruder and an outer layer forming extruder are connected to a coextrusion die is used. A polylactic acid resin and an additive as necessary are supplied to the core layer forming extruder and melt-kneaded, and another polylactic acid resin and, if necessary, an additive are added to the outer layer forming extruder. Is supplied and melt-kneaded. Each melt-kneaded product is joined in the die to form a multi-layered structure consisting of a cylindrical core layer and an outer layer covering the side surface of the core layer, and from the pores of the die attached to the die outlet at the tip of the extruder. The strand-like extrudate having a multilayer structure is extruded, cooled by submerging the strand-like extrudate, and then cut by a pelletizer so that the weight of the resin particles becomes a predetermined weight, thereby producing resin particles having a multilayer structure. . Alternatively, the resin particles can also be produced by cooling the strand-like extrudate having a multilayer structure after cutting or simultaneously with the cutting so that the weight of the resin particles becomes a predetermined weight.

The average weight per resin particle is preferably 0.05 to 10 mg, and more preferably 0.1 to 4 mg.
If the average weight is too light, the production of resin particles becomes special. On the other hand, when the average weight is too heavy, the density distribution of the obtained foamed particles may be increased, or the filling property during in-mold molding may be deteriorated.
As the shape of the resin particles, a columnar shape, a spherical shape, a prismatic shape, an elliptical spherical shape, a cylindrical shape, or the like can be adopted. Foamed particles obtained by foaming such resin particles have a shape substantially corresponding to the shape of the resin particles before foaming.

  In the step of obtaining the resin particles by melting and kneading the base resin with an extruder as described above to obtain resin particles, it is preferable to dry the polylactic acid resin, which is a constituent component of the base resin, in advance. In this case, deterioration due to hydrolysis of the polylactic acid resin can be suppressed. Moreover, in order to suppress degradation due to hydrolysis of the polylactic acid-based resin, a method of removing moisture from the polylactic acid-based resin by performing vacuum suction using an extruder with a vent port can be employed. By removing water from the polylactic acid-based resin, it is possible to suppress the generation of bubbles in the resin particles and improve the stability during extrusion production.

Next, the foaming agent impregnation step and the foaming step in the dispersion medium releasing foaming method will be described.
In the dispersion medium discharge foaming method, for example, the resin particles are dispersed and heated together with the dispersion medium and the physical foaming agent in the pressure resistant container, or the resin particles are dispersed and heated together with the dispersion medium in the pressure resistant container, and then physically foamed. The resin particles are impregnated with a physical foaming agent by press-fitting an agent into the pressure vessel to obtain expandable resin particles. Next, the foamable resin particles are expanded at a foamable temperature by releasing the foamable resin particles together with the dispersion medium under a pressure lower than that in the pressure resistant container, whereby foamed particles can be obtained.

A foaming aid can be added in advance to the resin particles. Examples of the foaming aid include inorganic substances such as talc, calcium carbonate, borax, zinc borate, aluminum hydroxide, silica, polytetrafluoroethylene, polyethylene wax, polycarbonate, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, Polymeric substances such as polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, silicone, methyl methacrylate copolymer, and crosslinked polystyrene can be employed.
Of the above foaming aids, polytetrafluoroethylene, polyethylene wax, cross-linked polystyrene and the like are preferable in the present invention, and hydrophobic polytetrafluoroethylene powder is more preferable.

  When adding a foaming aid to the base resin, the foaming aid can be kneaded into the base resin as it is, but in consideration of dispersibility, etc. It is preferable to knead the base resin.

  Since the apparent density and the cell diameter of the expanded particles of the present invention also change depending on the amount of the foaming aid added, a decrease in the apparent density (an improvement in the expansion ratio) and a uniform cell diameter can be expected. Usually, it is preferable to add 0.001 to 5 parts by weight of a foaming assistant to 100 parts by weight of the base resin, more preferably 0.005 to 3 parts by weight, and still more preferably 0.01 to 2 parts by weight. It is.

Since polylactic acid-based resins are easily hydrolyzed, it is preferable to avoid the hydrophilic substances as much as possible and to select and add hydrophobic substances as additives to the base resin. By adopting a hydrophobic foaming aid as the foaming aid, the effect as a foaming aid can be obtained while suppressing deterioration due to hydrolysis of the polylactic acid-based resin.
In this case, it is possible to reduce the apparent density (improve the foaming ratio) and make the bubble diameter uniform while sufficiently suppressing the hydrolysis of the polylactic acid resin.

In the dispersion medium releasing foaming method, as described above, for example, resin particles are dispersed in a dispersion medium such as water in a pressurizable closed container (for example, an autoclave), a dispersant is added, and a required amount of foaming agent is added. After impregnating and pressurizing and stirring under heating for a required time to impregnate the polylactic acid resin particles with the foaming agent, the container contents are released below the pressure inside the container to lower the pressure range, thereby foaming the resin particles, Expanded particles are obtained. At the time of this discharge, it is preferable to discharge the container with back pressure. Moreover, when obtaining expanded particles having a particularly low apparent density (high expansion ratio), the expanded particles obtained by the above-described method are subjected to a normal curing step under atmospheric pressure and can be pressurized again. And the pressure is increased by, for example, 0.01 to 0.10 MPa (G) with a pressurized gas such as air to increase the pressure in the foamed particles. Then, by using a heating medium such as hot air, steam or a mixture of air and steam, expanded particles having a lower apparent density can be obtained (this process is hereinafter referred to as two-stage foaming).
In addition, from the viewpoint that expanded particles having a low apparent density compared to the extrusion foaming method can be obtained, and foamed particles having excellent in-moldability and good physical properties can be obtained, the method for producing the expanded particles is as described above. A dispersion medium releasing foaming method in which the expandable resin particles are released to a low pressure region is preferable. In addition, the expanded particles can also be obtained by the gas-impregnated preliminary foaming method or the like in which foamable polylactic acid resin particles are heated and foamed by a preliminary foaming machine.

  As the dispersion medium for dispersing the resin particles, in addition to the above-described water, any material that does not dissolve the polylactic acid resin particles can be used. Examples of the dispersion medium other than water include ethylene glycol, glycerin, methanol, ethanol and the like. Water is preferable.

Further, when dispersing the resin particles in the dispersion medium, a dispersant can be added to the dispersion medium as necessary.
Examples of the dispersant include inorganic substances such as aluminum oxide, tricalcium phosphate, magnesium pyrophosphate, titanium oxide, zinc oxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, kaolin, mica, and clay, and polyvinylpyrrolidone. , Water-soluble polymer protective colloid agents such as polyvinyl alcohol and methylcellulose. In addition, as a dispersion aid, an anionic surfactant such as sodium dodecylbenzenesulfonate or sodium alkanesulfonate can be added to the dispersion medium.
These dispersing agents can be used in an amount of 0.05 to 3 parts by weight per 100 parts by weight of the resin particles, and these dispersing aids can be used in an amount of 0.001 to 0.3 parts by weight per 100 parts by weight of the resin particles. .

Examples of the blowing agent include hydrocarbons such as butane, pentane and hexane, organic physical blowing agents such as halogenated hydrocarbons such as trichlorofluoromethane, dichlorofluoromethane, tetrachlorodifluoroethane, and dichloromethane, carbon dioxide, nitrogen, Inorganic physical foaming agents such as air and water can be used alone or in combination of two or more. Among these physical foaming agents, it is preferable to use a physical foaming agent mainly composed of an inorganic physical foaming agent such as carbon dioxide, nitrogen or air. More preferred is carbon dioxide.
The term “inorganic physical foaming agent as a main component” means that the inorganic physical foaming agent in 100 mol% of the total physical foaming agent is 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more. Means that.

  The addition amount of the physical foaming agent can be appropriately adjusted according to the type of foaming agent, the blending amount of the additive, the apparent density of the intended foamed particles, and the like. For example, the inorganic physical foaming agent is used in an amount of generally 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight per 100 parts by weight of the base resin.

  Regarding temperature control in the blowing agent impregnation step, a sufficient time (usually 5 to 60 minutes) in the temperature range of the melting point −30 ° C. to the melting point −10 ° C. based on the melting point of the polylactic acid resin forming the resin particles. ) It is preferable to hold. By providing the holding step of the holding temperature and holding time, crystallization of the polylactic acid resin constituting the resin particles can be promoted, and the crystallinity of the resulting foamed particles can be stabilized to an appropriate value. The molding temperature range at the time of in-mold molding can be expanded, and as a result, the fusibility between the expanded particles is further improved. The holding time is further preferably 5 to 30 minutes, particularly 5 to 15 minutes from the viewpoint of inhibiting hydrolysis of the polylactic acid resin. The foaming temperature in the foaming step is usually performed in the temperature range from the melting point −50 ° C. to the melting point −10 ° C. based on the melting point of the polylactic acid resin forming the resin particles.

Next, the manufacturing method of the expanded particle molded object using the expanded particle of this invention is demonstrated. In manufacturing the foamed particle molded body, a known in-mold molding method can be employed.
For example, a compression molding method, a cracking molding method, a pressure molding method, a compression filling molding method, a normal pressure filling molding method (for example, Japanese Patent Publication No. 46-38359, Japanese Patent Publication No. 51) using a conventionally known foamed particle molding die. No. 22951, Japanese Patent Publication No. 4-46217, Japanese Patent Publication No. 6-22919, Japanese Patent Publication No. 6-49795, etc.).

  In-mold molding method that is usually preferably performed, the foam particles are filled into a cavity of a conventionally known thermoplastic resin foam particle molding mold that can be heated and cooled and that can be opened and closed and sealed, The foamed particles are expanded by supplying water vapor with a saturated vapor pressure of 0.01 to 0.25 MPa (G), preferably 0.01 to 0.20 MPa (G), and heating the foamed particles in a mold. Examples thereof include a batch type in-mold molding method in which the foamed particle molded body obtained by fusing and then cooling is taken out from the cavity, and a continuous in-mold molding method described later.

  As the method for supplying the water vapor, a conventionally known method in which heating methods such as one heating, reverse one heating, and main heating are appropriately combined can be adopted. In particular, a method of heating the expanded particles in the order of preliminary heating, one-side heating, reverse one-side heating, and main heating is preferable.

  The foamed particle molded body continuously supplies the foamed particles into a mold formed by a belt that moves continuously along the upper and lower sides of the passage, and the saturated vapor pressure is reduced when passing through the steam heating region. 0.01 to 0.25 MPa (G) of water vapor is supplied to expand and fuse the expanded particles, and then cooled by passing through a cooling region, and then the obtained expanded expanded particles are taken out from the passage, It can also be produced by a continuous in-mold molding method (for example, see JP-A-9-104026, JP-A-9-104027, JP-A-10-180888, etc.) which is sequentially cut into lengths.

  Prior to in-mold molding, foamed particles obtained by the above method are filled into a pressurizable sealed container, and foaming is performed by increasing the pressure in the foamed particles by pressurizing with a pressurized gas such as air. After the pressure inside the particles is adjusted to 0.01 to 0.15 MPa (G), the foamed particles are taken out from the container and molded in the mold, thereby further improving the in-mold moldability of the foamed particles. I can do it.

In addition, as described above, in order to obtain a foamed particle molded body that satisfies the following formula (1), which is particularly excellent in adhesion to a thermosetting resin, It is preferable to employ a curing process that holds for 3 to 24 hours under a temperature condition of -80 ° C.
70> [(Bfm: endo)-(Bfm: exo)]> 25 (1)

  The composite laminate of the present invention is obtained by bonding and laminating a thermosetting resin layer to the above-mentioned polylactic acid-based resin expanded particle molded body. Note that the thermosetting resin layer laminated and adhered to the foamed particle molded body may be completely covered with the foamed particle molded body, or may be laminated in a form in which a part of the foamed particle molded body is exposed, You may laminate | stack on the front surface and / or back surface of a molded object. Examples of the thermosetting resin constituting the thermosetting resin layer include unsaturated polyester resin, epoxy resin, phenol resin, polyamide resin, urea resin, melamine resin, polyimide resin, diallyl phthalate resin, etc. A saturated polyester resin is used.

  The thermosetting resin layer preferably contains a fiber material. As the thermosetting resin layer, what is called a fiber reinforced plastic (FRP) or a prepreg is known as a material containing a fiber substance. Although the thermosetting resin layer containing the fiber material is light, the strength, particularly the high bending strength, is enhanced, and the durability is excellent. Furthermore, it also serves to alleviate dimensional changes associated with the curing of the thermoplastic resin. However, the thermosetting resin layer in the present invention may not use a fiber material depending on the application.

  Examples of the fiber material include glass fiber, carbon fiber, vinylon fiber, polyester fiber, aromatic polyamide fiber, and phenol fiber, and glass fiber is generally used. Natural fibers such as bamboo fiber, kenaf, hemp, jute, sisal, ramie, and Kurrawa can also be used. The fiber length is usually 3 to 50 mm, preferably 6 to 25 mm. The content of the fiber substance is usually 0 to 60% by weight, preferably 5 to 40% by weight in the thermosetting resin layer.

The thermosetting resin layer in the present invention is preferably an unsaturated polyester resin, particularly preferably an unsaturated polyester and a crosslinkable monomer.
Examples of the unsaturated polyester include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, and fumaric acid, and acid anhydrides thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, Saturated dibasic acids such as sebacic acid, tetraphthalic anhydride, endomethylenetetrahydrophthalic acid or the like, and ethylene glycol, propylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 1, Esterification with 5-pentanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, adducts of bisphenol A with propylene oxide, polyhydric alcohols such as glycerin, trimethylolpropane, ethylene oxide, propylene oxide Also obtained by reaction It is. Dicyclopentadiene, cyclopentadiene-maleic acid adduct is used as an alternative to some of the raw materials described above. In addition, unsaturated polyester using a thermosetting resin using glycolic acid or carboxylic acid made from non-edible plants as raw materials and fumaric acid or maleic acid derived from petroleum (made by Nippon Iupika Co., Ltd. It is preferable from the viewpoint of environmental considerations.

  Examples of the crosslinkable monomer include styrene, vinyl toluene, α-methyl styrene, chloro styrene, dichloro styrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylo Vinyl compounds such as nitriles or allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate, triallyl cyanurate, vinyl monomers or vinyl oligomers that can be cross-linked with unsaturated polyesters, etc. are used alone or in combination. In general, styrene is used.

  The unsaturated polyester is dissolved in a crosslinkable monomer and used as an unsaturated polyester resin. As described above, the unsaturated polyester resin contains a fiber material as needed, and is laminated and cured on the surface of the polylactic acid resin foamed particle molded body, thereby being adhered and laminated on the surface of the foamed particle molded body. It becomes a thermosetting resin layer.

  Moreover, a filler, a hardening | curing agent, a mold release agent, a low shrinkage agent, and a thickener can be mix | blended with this unsaturated polyester resin as needed.

  Examples of the filler include calcium carbonate, aluminum hydroxide, talc, clay, barium sulfate, alumina, cinnabar sand, silica powder, glass beads, glass powder, and cold water stone. used. Usually calcium carbonate is used.

  Examples of the curing agent include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, peroxyperbenzoate, cumene hydroperoxide, tertiary butyl perbenzoate, peroxyketal, and dicumyl peroxide.

  Examples of the release agent include conventional internal release agents such as higher fatty acids such as stearic acid and metal salts thereof, higher fatty acid esters, alkyl phosphate esters, and carnauba wax.

  Examples of the low shrinkage agent include polystyrene, polyvinyl acetate, polyethylene, polypropylene, polymethyl methacrylate, styrene-butadiene block copolymer, and saturated polyester.

  As the thickener, the unsaturated polyester resin is thickened by chemically bonding with a hydroxyl group, carboxyl group, ester bond, etc. of the unsaturated polyester to form a linear or partially cross-linked bond to increase the molecular weight. Examples thereof include polyisocyanate compounds, metal alkoxides, divalent metal oxides, and divalent metal hydroxides.

  Examples of the polyisocyanate compound include diisocyanates such as toluene diisocyanate, 4, 4 ′ diphenylmethane diisocyanate and modified compounds thereof, metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, magnesium oxide, calcium oxide, Examples thereof include bivalent metal oxides such as beryllium oxide and divalent metal hydroxides such as calcium hydroxide. The blending amount of this thickener is, for example, 0.05 to 10.0% by weight.

  Furthermore, at least one of a pigment, a viscosity reducing agent, and an antifoaming agent may be added to the unsaturated polyester composition as necessary.

  In the present invention, when forming a thermosetting resin layer bonded and laminated on the surface of the polylactic acid-based resin expanded particle molded body, hand lay-up molding, resin transfer molding (RTM), sheet molding compound molding ( Known molding methods such as SMC) and bulk molding compound molding (BMC) can be used.

The composite laminate of the present invention can be applied to conventionally known FRP applications such as bathtubs, water tanks, temporary toilets, chairs, waterproof pans, vehicle panels, vehicle bodies, ship bodies, floats, surfboards, snowboards, helmets, and the like. New applications such as vehicle door panels and solar power generation equipment can be expected.
In addition, the composite laminate of the present invention can be obtained by adopting a material having a higher plant-derived component ratio as a thermosetting resin, or by using natural fibers as a fiber material, so that the base material of the composite laminate can be polylactic acid. Since it is a resin-based foamed resin molded body, it is particularly excellent in consideration of the environment.

  Next, the present invention will be described in more detail with reference to examples.

<Manufacture of polylactic acid-based resin expanded particles>
An extruder provided with a co-extrusion die for forming a multilayer strand on the outlet side of an extruder for forming a core layer having an inner diameter of 65 mm and an extruder for forming an outer layer having an inner diameter of 30 mm was used.
Crystalline polylactic acid resin: “Terramac TP-4000E” (modified with carbodiimide compound, melting point: 168 ° C., MFR (190 ° C./2.16 kgf): 4.6 g / 10 min) supplied to the extruder for forming the core layer The crystalline polylactic acid resin: “Terramac TP-4001E” manufactured by Unitika (modified with a carbodiimide compound, melting point: none, MFR (190 ° C./2.16 kgf): 6.0 g / 10 min) is supplied to the outer layer forming extruder. And kneaded. The melt-kneaded product is introduced into the co-pressing die at a weight ratio of core layer supply amount / outer layer supply amount = 90/10, merged in the die, and from the pores of the die attached to the tip of the extruder, the core Co-extruded as a multilayer strand having an outer layer formed on the side surface of the layer, the co-extruded strand was cooled with water, cut to a weight of approximately 2 mg with a pelletizer, and dried to obtain multilayer resin particles.
In addition, polytetrafluoroethylene powder (trade name: TFW-1000, manufactured by Seishin Enterprise Co., Ltd.) is supplied in a master batch so that the content of the polylactic acid resin in the core layer is 1000 ppm by weight as a foam regulator. did.

Next, polylactic acid-based resin expanded particles were produced using the resin particles.
First, 1 kg of the resin particles obtained as described above was charged into a 5 L sealed container equipped with a stirrer together with 3 L of water as a dispersion medium, and 0.1 parts by weight of aluminum oxide as a dispersant was further added to the dispersion medium. Then, 0.01 part by weight of surfactant (trade name: Neogen S-20F, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., sodium alkylbenzene sulfonate) was added. Next, the temperature was raised to 140 ° C. with stirring, and carbon dioxide as a blowing agent was injected into the sealed container until the pressure reached 2.8 MPa (G), and the temperature was maintained for 15 minutes. Next, the temperature was raised to the foaming temperature, carbon dioxide was injected until the pressure reached 3.0 MPa (G), and the foaming temperature was held at 145 ° C. for 15 minutes. Thereafter, the contents were released under atmospheric pressure while applying back pressure with carbon dioxide to obtain expanded polylactic acid resin particles having an apparent density of 80 g / L. In addition, the addition amount (parts by weight) of the dispersant and the surfactant is an amount with respect to 100 parts by weight of the polylactic acid resin particles.

  The endothermic amount (Br: endo) of the obtained expanded particles was 38 J / g, the endothermic amount (Brc: endo) at the center of the expanded particles was 41 J / g, and the endothermic amount (Brs: endo) of the surface layer of the expanded particles was 32 J. / G, the endothermic amount (Bfc: endo) at the center of the expanded particle is 41 J / g, the calorific value (Bfc: exo) at the center of the expanded particle is 18 J / g, and the difference [(Bfc: endo) − (Bfc: exo) ] Is 20 J / g, the softening point (A) of the polylactic acid resin constituting the core layer is 157 [° C.] and the softening point (B) of the polylactic acid resin constituting the outer layer is 58 [° C.], and the difference [( A)-(B)] was 99 ° C.

<Production of Polylactic Acid Resin Expanded Particle Molded Body 1>
A foamed particle molded body was produced using the foamed particles.
First, foamed particles having an internal pressure of 0.05 MPa (G) are filled into a flat plate mold having a length of 200 mm × width of 250 mm × thickness of 20 mm, and subjected to in-mold molding by pressure molding by steam heating to form plate-shaped foamed particles. A molded body was obtained. The heating method is to supply steam for 5 seconds with the double-sided drain valve open, perform preheating (exhaust process), and then supply steam from the moving side for 5 seconds with the fixed drain valve open. Next, steam was supplied for 10 seconds from the stationary side with the moving side drain valve opened, and then heated at a molding heating steam pressure (vapor pressure) of 0.08 MPa (G).

After completion of heating, the pressure was released, and after cooling with water until the surface pressure due to the foaming force of the molded body decreased to 0.02 MPa (G), the mold was opened and the molded body was taken out of the mold. The obtained molded body was cured in an oven at 40 ° C. for 15 hours, then cured in an oven at 70 ° C. for 15 hours, and then gradually cooled to room temperature. In this way, a foamed particle molded body 1 having a thickness of 20 mm was obtained.
The obtained foamed particle molded body has an endothermic amount (Bfm: endo) of 39 J / g, the foamed particle molded body has a heat generation amount (Bfm: exo) of 0 J / g, and the difference [(Bfm: endo) − (Bfm: exo). ] Was 39 J / g.

  The resulting expanded particle molded body has a bulk density of 65 g / L, a shrinkage rate of 1.2%, a fusion rate of 90%, a heating dimensional change rate (120 ° C.) of 0.2%, and an excellent appearance. It was a foamed particle molded body in which the particle gap due to secondary foaming failure of the foamed particles was not noticeable on the surface.

<Production of Polylactic Acid Resin Expanded Particle Molded Body 2>
Except that the foamed particle molded body obtained by in-mold molding was cured in an oven at 40 ° C. for 15 hours, then cured in an oven at 50 ° C. for 6 hours, and then gradually cooled to room temperature. The foamed particle molded body 2 having a thickness of 20 mm was obtained in the same manner as the production of the lactic acid resin expanded particle molded body 1.
The obtained foamed particle molded body has an endothermic amount (Bfm: endo) of 39 J / g, the foamed particle molded body has a heat generation amount (Bfm: exo) of 10 J / g, and the difference [(Bfm: endo) − (Bfm: exo). ] Was 29 J / g.
The resulting expanded particle molded body 2 has a bulk density of 65 g / L, a shrinkage rate of 0.6%, a fusion rate of 90%, a heating dimensional change rate (120 ° C.) of 2.8%, and an excellent appearance. It was a foamed particle molded body in which the particle gap due to the secondary foaming failure of the foamed particles was not noticeable on the surface.

In addition, the measuring method and evaluation method of various physical properties of a foamed particle molded body are as follows.
"Fusion rate"
The fusion rate was determined based on the ratio (the fusion rate) of the number of foam particles whose material was destroyed among the foam particles exposed on the fracture surface when the foamed particle molded body was broken. Specifically, the foamed particle molded body was cut by about 10 mm in the thickness direction of the foamed particle molded body with a cutter knife, and then the foamed particle molded body was broken from the cut portion. Next, the number (b) of foam particles present on the fracture surface and the number (b) of the foam particles whose material was destroyed were measured, and the ratio (b / n) of (b) and (n) was expressed as a percentage. It was set as the fusion rate (%).

"Bulk density of molded body"
The bulk density of the foamed particle molded body was measured as follows.
The bulk volume was determined from the external dimensions of the foamed particle molded body that was allowed to stand for 24 hours or more in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Next, the weight (g) of the foamed particle compact was precisely weighed. The bulk density (g / L) of the foamed particle molded body was determined by dividing the weight of the foamed particle molded body by the bulk volume and converting the unit.

"Internal pressure"
The internal pressure of the foamed particles when producing the foamed particle molded body or two-stage foaming is a part of the foamed particles immediately before filling the in-mold molding machine or just before the two-stage foaming machine is charged (hereinafter referred to as a foamed particle group). Was measured as follows.
Within 60 seconds after removing the foam particles from the pressurized tank immediately before filling the in-mold molding machine whose internal pressure has been increased in the pressurized tank or just before charging the two-stage foaming machine, the expanded particles are not allowed to pass through, but the air It was housed in a bag of about 70 mm × 100 mm with a large number of needle holes of a size that can pass freely, and moved to a constant temperature and humidity chamber under an atmospheric pressure with an air temperature of 23 ° C. and a relative humidity of 50%. Subsequently, a bag containing foam particles was placed on the balance in the constant temperature and humidity chamber, and the weight was read. The measurement of the weight was performed 120 seconds after the above-mentioned expanded particle group was taken out from the pressurized tank. The weight at this time was defined as Q (g). Subsequently, the bag containing the expanded particles was left in the same temperature and humidity chamber for 10 days. Since the pressurized air in the expanded particles permeates the bubble wall and escapes to the outside as time passes, the weight of the expanded particles group decreases accordingly, and after 10 days, the weight has reached equilibrium. Stable. Therefore, after 10 days, the weight of the bag containing the expanded particle group was measured again in the same temperature and humidity chamber, and this weight was defined as U (g). The difference between Q (g) and U (g) was defined as the increased air amount W (g), and the internal pressure P (MPa) of the expanded particles was calculated by the following equation (6). The internal pressure P corresponds to a gauge pressure.

P = (W ÷ M) × R × T ÷ V (6)
However, in the above formula, M is the molecular weight of air, and here, a constant of 28.8 (g / mol) is adopted. R is a gas constant, and here, a constant of 0.0083 (MPa · L / (K · mol)) is adopted. T means an absolute temperature, and since an atmosphere of 23 ° C. is adopted, it is a constant of 296 (K) here. V means the volume (L) obtained by subtracting the volume of the base resin in the expanded particle group from the apparent volume of the expanded particle group.

The apparent volume of the expanded particles is determined by submerging the entire amount of expanded particles taken out of the bag after 10 days of curing into water in a graduated cylinder containing 100 cm ^{3 of} 23 ° C. water immediately in the same temperature and humidity chamber. The volume Y (cm ³ ) of the expanded particle group is calculated from the increment of the scale at the time of making it, and this is obtained by converting this to liter (L) units. The volume (L) of the base resin occupying in the foam particle group is the foam particle weight (difference between U (g) and the weight Z (g) of the bag having a large number of needle holes). It is determined by dividing the particle by the density (g / cm ³ ) of the resin obtained by defoaming the particles with a heat press. In this case, the apparent density (g / cm ³ ) of the expanded particle group is obtained by dividing the weight of the expanded particle group (difference between U (g) and Z (g)) by the volume Y (cm ³ ). Desired.
In the above measurement, the foamed particle group weight (difference between U (g) and Z (g)) is 0.5000 to 10.0000 g, and the volume Y is 50 to 90 cm ^3. A group of expanded particles is used.

"Heat dimensional change rate"
In accordance with the thermal stability described in JIS K6767 (1999) (dimensional stability at high temperature, method B), a test piece was placed in a gear oven maintained at 120 ° C. and heated for 22 hours. The sample was then taken out, left in a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity for 1 hour, and the heating dimensional change rate was determined from the dimensions before and after heating using the following formula.
Heating dimensional change rate (%) = (dimension after heating−dimension before heating) / dimension before heating × 100

<Manufacture of composite laminate>
Examples 1-4
A fiber-reinforced unsaturated polyester composition is laminated on the surface of the foamed particle molded body 1 (however, the foamed particle molded body 2 was used in Example 4) and bonded to form a thermosetting resin layer. Thus formed.
A flat plate made of aluminum having a surface coated with polytetrafluoroethylene (Teflon) was prepared.
<1> Methyl ethyl ketone peroxide was added as a curing agent to unsaturated polyester “Biomap BM-13” manufactured by Nippon Iupika Co., Ltd. The obtained unsaturated polyester resin was applied to the Teflon surface of the flat plate by a hand lay-up method.
<2> Next, the fiber mat shown in Table 1 having a size of 200 mm × 150 mm was placed on the surface coated with the unsaturated polyester resin.
<3> An unsaturated polyester resin added with the same curing agent as described above was coated and impregnated by the hand lay-up method.
After the steps <1> to <3> were repeated to form two plies, a 200 mm × 150 mm surface of a polylactic acid resin foamed resin mold (200 mm × 150 mm × 20 mm) was immediately placed thereon.

continue
<1> ′ An unsaturated polyester resin to which the same curing agent as described above was added was applied to the upper surface (the surface on which the unsaturated polyester resin was not applied) of the in-mold molded body by a hand lay-up method.
<2> ′ Further, a fiber mat shown in Table 1 was placed thereon.
<3> ′ An unsaturated polyester resin added with the same curing agent as described above was coated and impregnated by the hand lay-up method.
After repeating the steps <1> ′ ′ to <3> ′ to make two plies, an aluminum flat plate coated with Teflon (weight 1 kg) was immediately placed and allowed to react and cure the unsaturated polyester resin. After reaction hardening, the aluminum flat plate is peeled off, and a composite laminate (FRP laminate) comprising glass fiber reinforced unsaturated polyester resin cured product (FRP) / molded product / glass fiber reinforced unsaturated polyester resin cured product (FRP) is prepared. Obtained.

Example 5
Using two carbon fiber epoxy resin prepregs “Pyrofil TR3110-830IMPY” manufactured by Mitsubishi Rayon Co., Ltd., the polylactic acid resin foamed resin in-mold product (200 mm × 150 mm × 20 mm) is sandwiched between the two, and 80 ° C. After being cured by holding for 1 hour under a 1 kgf press pressure on a heat press heated to 1, a composite laminate in which a carbon fiber reinforced epoxy resin is laminated and bonded to the surface of the polylactic acid foamed particle molded body is removed from the heat press. Obtained.

Comparative Example 1
Without using the foamed particle molded body, 5 plies of the same fiber-reinforced unsaturated polyester as in Example 1 were used to obtain a plate-shaped molded body.

Comparative Example 2
Except for the foamed particle molded body, a polystyrene resin foamed particle molded body having a bulk density of 65 g / L, a fusion rate of 90%, a good appearance, and a particle gap due to poor secondary foaming of the foamed particles on the surface is not used. Then, a thermosetting resin layer made of fiber-reinforced unsaturated polyester was laminated by the same method as in Example 1 to obtain a composite laminate.

Comparative Example 3
As the foamed particle molded body, a polypropylene resin foamed particle molded body with a bulk density of 65 g / L, a fusion rate of 90%, a good appearance, and a particle gap due to secondary foaming failure of the foamed particles is not noticeable on the surface. Then, a thermosetting resin layer made of fiber-reinforced unsaturated polyester was laminated by the same method as in Example 1 to obtain a composite laminate.

  Examples, basis weight of composite laminates obtained in comparative examples, adhesion between foamed particle molded body and thermosetting resin layer, shape retention of foamed particle molded body after composite, heat resistance after composite, 1 mm deflection The load (kPa) is shown in Table 1.

"Heat-resistant"
After measuring the dimension (L [mm]) of the foamed particle molded body part of the composite laminate, it was placed in a gear oven kept at 150 ° C., heated for 22 hours, taken out, and kept constant at 23 ° C. and 50% relative humidity. for 1 hour in a moist chamber, again to determine the dimensional change upon heating by have measurements dimension (L a _[mm]) of the foamed bead molded article portion following equation (7).
Heating dimensional change rate (%) = (L−L _A ) / L × 100 (7)
As a result, when the rate of change in heating dimension of the foamed particle molded body portion is less than 2% and the warp of the composite is not recognized as “◯”, the rate of change in heating dimension of the foam molded body portion is 2 % Or more and less than 4% was evaluated as “Δ”, and the rate of change in the heating dimension of the foamed particle molded body portion was 4% or more, or the case where the warpage of the composite was observed was evaluated as “x”.

"Adhesion between thermosetting resin and foamed particle molding"
The composite / cured layered composite was peeled off from the interface, and the foamed particle molded body was destroyed when the material was peeled off, and the foamed particle molded body was peeled off without breaking the material was marked as “X”. .

"Shape retention of foamed particle compact"
“○” indicates that there is no change in the shape of the foamed particle molded body of the composite laminate after completion of the composite and curing from the state before lamination, “△” indicates that the foamed particle molded body is swollen or shrunk; The case where thinning or chipping due to dissolution or melting was observed in the molded body was designated as “x”.

Claims (6)

  A composite laminate comprising a polylactic acid-based resin expanded particle molded body and a thermosetting resin layer adhered and laminated on the surface of the expanded particle molded body. The polylactic acid-based resin foamed particle molded body has an endothermic amount (Bfm) of the foamed particle molded body obtained under the following condition 1 based on the heat flux differential scanning calorimetry described in JIS K7122 (1987). : Endo) [J / g] and calorific value (Bfm: exo) [J / g] satisfy the following formula (1): The composite laminate according to claim 1.
70> [(Bfm: endo)-(Bfm: exo)]> 25 (1)
Condition 1
[Measurement of endotherm and calorific value]
The measured values of the endothermic amount (Bfm: endo) and the calorific value (Bfm: exo) were obtained by measuring 1 to 4 mg of a measurement sample collected from the foamed particle molded body as described in JIS K7122 (1987). In accordance with the measurement method, the value is determined based on the DSC curve obtained when heating and melting from 23 ° C. to 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min. The polylactic acid-based resin expanded particles constituting the polylactic acid-based resin expanded particle molded body are obtained under the following condition 2 in accordance with the heat flux differential scanning calorimetry described in JIS K7122 (1987). The endothermic amount of the entire expanded particle (Br: endo) [J / g], the endothermic amount of the expanded particle surface layer (Brs: endo) [J / g], and the endothermic amount of the center of the expanded particle (Brc: endo) [ J / g] satisfies the following formulas (2) and (3): The composite laminate according to claim 1 or 2.
(Br: endo)> 25 (2)
(Brc: endo)> (Brs: endo) ≧ 0 (3)

Condition 2
[Measurement sample adjustment]
(Sample for measuring the endothermic amount of the foam particle surface)
The surface layer portion including the surface of the expanded particles is cut to collect the surface layer portion to obtain a measurement sample. In the cutting process, a measurement sample having a weight of 1/6 to 1/4 of the weight of the expanded particles before the cutting process is collected from the entire surface of one expanded particle.

(Sample for measuring endotherm at the center of expanded particles)
The entire surface of the foamed particles is removed by cutting, and the remainder of the foamed particles having a weight of 1/5 to 1/3 of the weight of the foamed particles before the cutting treatment is taken as a measurement sample.

[Measurement of endotherm]
The measured value of each endothermic amount, (Br: endo), (Brs: endo), or (Brc: endo) is measured with the polylactic acid resin expanded particles, the measurement sample collected from the surface layer of the expanded particles, or the expanded In accordance with the heat flux differential scanning calorimetry described in JIS K7122 (1987), 1 to 4 mg of a measurement sample collected from the center of the particle is heated and melted to a temperature 30 ° C. higher than the melting peak end temperature. After maintaining at that temperature for 10 minutes, cooling to 110 ° C. at a cooling rate of 2 ° C./min, holding at that temperature for 120 minutes, and then cooling to 40 ° C. at a cooling rate of 2 ° C./min. And a value obtained on the basis of a DSC curve obtained when heating and melting to a temperature 30 ° C. higher than the end of the melting peak at a heating rate of 2 ° C./min.   The polylactic acid-based resin expanded particles forming the polylactic acid-based resin expanded particle molded body are composed of a core layer composed of a polylactic acid-based resin, and a polylactic acid-based resin located on the surface side of the core layer. The difference between the softening point (A) [° C.] of the polylactic acid resin constituting the core layer and the softening point (B) [° C.] of the polylactic acid resin constituting the outer layer [(A )-(B)] exceeds 0 ° C. and is equal to or lower than 105 ° C. The composite laminate according to claim 1,   The composite laminate according to any one of claims 1 to 4, wherein the thermosetting resin layer contains a fiber substance.   The composite laminate according to any one of claims 1 to 5, wherein the thermosetting resin constituting the thermosetting resin layer is an unsaturated polyester resin.