JP3067511B2 - Phenolic resin laminate and method for producing phenolic resin molded article using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic resin laminate used for automobile parts such as interior parts of automobiles and various other molded articles and a method for producing a phenolic resin molded article obtained by using the same. Things.

[0002]

2. Description of the Related Art SMC (sheet molding compound) comprising a phenol resin precondensate and glass fiber
A phenolic resin molded article obtained by heating and press molding into a desired shape is used for automobile interior materials, automobile outer panels, automotive parts such as spoilers, bathroom wall panels, housing parts such as ceiling materials, and OA equipment. Widely used for various covers such as covers. In particular, a phenol resin molded article having a low specific gravity, which is obtained by heating and pressing an SMC containing a foaming agent, is used as an interior material of an automobile. Although the phenolic resin molded article having a low specific gravity is light in weight and excellent in strength, it is required to further improve heat insulation as an interior material of an automobile.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a molded article which is lightweight, has excellent strength, and has improved heat insulation. An object of the present invention is to provide a phenolic resin laminate and a method for producing a phenolic resin molded article obtained by using the phenolic resin laminate.

[0004]

A phenolic resin laminate according to claim 1 of the present invention has a vertically open cell (21).
A layer (1a) of SMC comprising a phenolic resin precondensate containing a foaming agent and a chopped strand of glass fiber is formed on and under a layer of a honeycomb sheet material (2) made of paper having The SMC has a fiber length of 10 to 5 on a phenolic resin composition mixed with a blowing agent.
Sprinkle chopped strands of 0mm glass fiber,
It is characterized by being obtained.

[0005] The phenolic resin laminate according to claim 2 is
The longest distance of the diameter of the hole opened above and below the cell (21) of the honeycomb sheet material (2) is 3 to 30 mm.

[0006] The phenolic resin laminate according to claim 3 is:
A nonwoven fabric (3) layer is formed on the upper and lower surfaces of the SMC layer (1a).

According to a fourth aspect of the present invention, there is provided a method for producing a phenolic resin molded article, wherein the phenolic resin laminate is subjected to heat and pressure molding.

Hereinafter, the present invention will be described in detail. FIG.
FIG. 1 is a partially broken perspective view showing an example of the phenolic resin laminate of the present invention, and FIG. 1A is a cross-sectional view of the phenolic resin laminate shown in FIG. 3. As shown in the figure, the SMC layers (1a) are formed above and below the honeycomb sheet material (2) constituting the phenolic resin laminate of the present invention. This phenolic resin laminate can be formed, for example, by sandwiching the honeycomb sheet material (2) above and below with the SMC (1). At this time, even if the SMC layer (1a) of the phenolic resin laminate is formed by laminating the SMC (1) one by one on the upper and lower surfaces of the layer of the honeycomb sheet material (2), a plurality of They may be stacked one by one.

SMC forming the above-mentioned SMC layer (1a)
(1) is a sheet comprising a phenolic resin precondensate containing a foaming agent and a chopped strand of glass fiber. Examples of the phenol resin used for the phenol resin precondensate constituting the SMC (1) include novolak type or resol type obtained by reacting various phenol compounds such as phenol, alkylphenol, biphenol, bisphenol A and bisphenol F with formaldehyde. Phenolic resins can be used. Further, the phenol resin precondensate contains a foaming agent. Examples of the foaming agent include nitrosotetramines such as dinitrosopentamethylenetetramine (DPT), benzenesulfonylhydrazide, p
-Sulfonyl hydrazides such as -toluenesulfonyl hydrazide and p, p'-oxybisbenzenesulfonyl hydrazide; and azo compounds such as azobisisobutyronitrile and azodicarbonamide can be appropriately used. Further, to the phenolic resin initial condensate, a curing agent, a curing accelerator, a foaming aid, a flame retardant, a viscosity modifier, a coloring agent, a foam stabilizer, a surfactant, and an additive such as a filler are appropriately added. Is also good.

[0010] As the chopped strand of glass fiber constituting the SMC layer (1a), a fiber having a fiber length of 10 to 50 mm is used.

The above-mentioned S forming the above-mentioned SMC layer (1a)
An example of a method for producing MC (1) will be described. For example, a phenol resin obtained by mixing the above-mentioned phenol resin, a foaming agent, and an appropriate additive on a release film made of polypropylene, polyester, vinyl, or the like. The composition is applied, the chopped strands of the glass fiber are sprayed on the phenol resin composition, and the sheet on which the release film is further placed is placed at a temperature of room temperature to 70 ° C., preferably 30 to 50 ° C. After primary curing for 1 to 7 days in the above range, SMC (1) with a release film in which the phenol resin composition has become a phenol resin precondensate in the B-stage state is obtained. The SMC (1) is used by peeling the release film. The SMC (1) forming the SMC layer (1a) of the present invention preferably has a fiber ratio of 5 to 50% by weight (resin ratio of 95 to 50% by weight). Furthermore, the above SMC
It is preferable to use (1) having a basis weight of 200 to 2000 g / m ² .

The honeycomb sheet material (2) made of paper is as follows.
It has a cell (21) opened vertically, and the longest distance of the diameter of the hole opened vertically of the cell (21) is preferably 3 to 30 mm. When the pore diameter of the cell (21) is less than 3 mm, the specific gravity of the honeycomb sheet material (2) becomes large, which is not preferable. Further, when the phenolic resin laminate of the present invention is subjected to heat and pressure molding, the molten phenolic resin precondensate constituting the layer (1a) of the SMC does not easily enter the cell (21).
If the pore diameter of the cell (21) exceeds 30 mm, the strength of the honeycomb sheet material (2) decreases. The honeycomb sheet material (2) is made of paper.

FIG. 1 (b) is a sectional view showing an example of a phenolic resin molded article obtained by the method for producing a phenolic resin molded article of the present invention. This phenolic resin molded product is obtained by subjecting the phenolic resin laminate to heat and pressure molding. That is, when the phenol resin laminate is set in a molding die having a predetermined shape and heated and pressed, the phenol resin precondensate constituting the layer (1a) of the SMC is melted and the honeycomb sheet material ( The phenol resin precondensate is secondarily cured into the cell (21) of 2) to form an SMC layer (1b). As a result, a phenol resin molded body in which the SMC layer (1b) and the honeycomb sheet material (2) are integrated is obtained. At this time, the air (22) in the cell (21) of the honeycomb-shaped sheet material (2) loses its escape place and
The layer of the honeycomb-shaped sheet material (2) is confined in 1) and contains a large amount of air (22). Therefore, by the layer of the honeycomb-shaped sheet material (2), the phenolic resin molded article is reduced in weight and is provided with heat insulating properties. Further, in the phenolic resin molded article, since the honeycomb-shaped sheet material (2) has a structure in which the cells (21) are vertically opened and is structurally robust against a load from the vertical direction, Has excellent strength. In the method for producing a phenolic resin molded article of the present invention, a plurality of the phenolic resin laminates may be laminated and used according to a desired thickness or weight of the phenolic resin molded article. The molding conditions of the heat and pressure molding are as follows.
It is preferable to perform the treatment at 90 ° C. and a pressure of up to 400 kg / cm ² .

FIG. 2C is a sectional view showing another example of the phenolic resin laminate of the present invention. As shown in FIG. 2 (c), this phenolic resin laminate was formed on the upper and lower surfaces of the honeycomb-shaped sheet material (2).
Further, a layer of nonwoven fabric (3) is formed on the upper and lower surfaces of a). The phenolic resin laminate as shown in FIG. 2C can be formed by laminating nonwoven fabrics (3) on the upper and lower surfaces of the SMC (1) layer. Further, when the phenol resin laminate is molded under heat and pressure as described above, a phenol resin molded article having a nonwoven fabric (3) layer formed on the surface can be obtained as shown in FIG. 2 (d). That is, in the phenolic resin laminate, a phenolic resin molded article having the above-mentioned nonwoven fabric (3) as a decorative surface can be obtained by a single molding, and the labor of gluing the decorative surface later and bonding can be omitted.

[0015]

The phenolic resin laminate according to claim 1 of the present invention is a phenolic resin precondensate containing a foaming agent above and below a layer of a honeycomb sheet material (2) having vertically opened cells (21). And an SMC layer (1a) composed of a glass fiber chopped strand and a phenolic resin molded body obtained by heating and pressing the phenolic resin laminate. The layer of the honeycomb-shaped sheet material is integrated with the cells of the honeycomb-shaped sheet material in a state where air is held therein. That is,
The phenolic resin precondensate constituting the heated and melted SMC layer (1a) penetrates into the cells (21) of the honeycomb sheet material (2) from the upper and lower openings of the cells (21). As the air hardens, the air in the cell (21) loses its escape space and is trapped in the cell (21). Therefore, the phenolic resin molded article is lightweight, and the layer of the honeycomb-shaped sheet material (2) containing a large amount of air exhibits an excellent heat insulating effect. In addition, the phenolic resin molded article is superior because the honeycomb-shaped sheet material (2) has a structure in which the cells (21) are opened up and down and is structurally robust against a load from above and below. Has strength.

The phenolic resin laminate according to claim 2 is
Since the longest distance of the diameter of the hole opened above and below the cell (21) of the honeycomb-shaped sheet material (2) is within a range of 3 to 30 mm, when the phenol resin laminate is heated and pressed, the weight is reduced. And a phenolic resin molded article having both excellent strength.

The phenolic resin laminate according to claim 3 is
Since the layers of the nonwoven fabric (3) are formed on the upper and lower surfaces of the layer (1a) of the SMC, a phenolic resin molded article having the nonwoven fabric (3) as a decorative surface can be obtained by one molding, The work of gluing the decorative surface later by gluing or the like can be omitted.

In the method for producing a phenolic resin molded product according to the fourth aspect, the phenolic resin laminate is heat-pressed, so that the obtained phenolic resin molded product is lightweight, has excellent strength, and has heat insulating properties. Is improved.

[0019]

Embodiments of the present invention will be described below. (Preparation of phenolic resin composition) 100 parts by weight of a resole type liquid phenolic resin, 4 parts by weight of zinc stearate as a release agent, 3 parts by weight of dinitrosopentamethylenetetramine (DPT) as a foaming agent, and as a surfactant A phenol resin composition was obtained by blending 2 parts by weight of the polyether-modified silicone. This phenol resin composition was used in the following Examples and Comparative Examples. (Example 1) The above-mentioned phenol resin composition was applied on a release film made of polyester, glass fibers having an average fiber length of 25 mm were sprayed from the upper surface thereof, and the release film was further placed thereon. The obtained sheet with a release film was primarily cured at 40 ° C. for 2 days to bring the resol type liquid phenol resin into a B-stage state. The fiber ratio was 30% by weight, the resin ratio was 70% by weight, and the basis weight was 50%. 90
An SMC with a release film of 0 g / m ² was obtained. This SM
After peeling the release film from C, the basis weight was 200 g /
m ^2, the cell size 13 mm, to form a phenolic resin laminate by laminating the upper and lower surfaces of a paper honeycomb sheet material. This phenolic resin laminate was set in a press molding machine, and was heated and pressed under molding conditions of 170 ° C., 10 kg / cm ² , and 120 seconds to obtain a flat phenolic resin molded article having a thickness of 5.0 mm. (Example 2) The above-mentioned phenol resin composition was applied on a release film made of polyester, glass fibers having an average fiber length of 25 mm were sprayed from the upper surface thereof, and the release film was further placed thereon. The obtained sheet with a release film was primarily cured at 40 ° C. for 2 days to bring the resol type liquid phenol resin into a B-stage state. The fiber ratio was 30% by weight, the resin ratio was 70% by weight, and the basis weight was 50%. 14
An SMC with a release film of 00 g / m ² was obtained. This S
After peeling the release film from the MC, the basis weight is 200 g / m.
^2. Laminated on both the upper and lower surfaces of a paper honeycomb sheet material having a cell size of 13 mm, and further, laminated a polyester fiber nonwoven fabric with a basis weight of 30 g / m ² on the upper and lower surfaces of the SMC to form a phenolic resin laminate. did. This phenolic resin laminate was set in a press molding machine,
Heat and pressure molding was performed under the molding conditions of kg / cm ² and 120 seconds to obtain a flat phenolic resin molded article having a thickness of 5.0 mm. (Example 3) The above-mentioned phenol resin composition was applied on a release film made of polyester, glass fibers having an average fiber length of 25 mm were sprayed from the upper surface thereof, and the release film was further placed thereon. The obtained sheet with a release film was primarily cured at 40 ° C. for 2 days to bring the resol type liquid phenol resin into a B-stage state. The fiber ratio was 30% by weight, the resin ratio was 70% by weight, and the basis weight was 50%. 50
An SMC with a release film of 0 g / m ² was obtained. This SM
After peeling the release film from C, the basis weight was 200 g /
m ² , 13 mm cell size, laminated on both upper and lower surfaces of a paper-made honeycomb sheet material, and further, laminated on the upper and lower surface sides of the SMC, a polyester fiber nonwoven fabric with a basis weight of 30 g / m ² to form a phenol resin laminate. Formed. This phenolic resin laminate was set on a press molding machine,
It was heated and pressed under the conditions of 0 kg / cm ² and 120 seconds to obtain a flat phenolic resin molded article having a thickness of 100 mm. (Comparative Example 1) The above-mentioned phenolic resin composition was applied on a polyester release film, glass fibers having an average fiber length of 25 mm were sprayed from the upper surface thereof, and the release film was further placed thereon. The sheet with the release film was primarily cured at 40 ° C. for 2 days to bring the resol type liquid phenol resin into the B-stage state. The fiber ratio was 30% by weight, the resin ratio was 70% by weight, and the basis weight was 300.
An SMC with a release film of 0 g / m ² was obtained. This SM
After peeling the release film from C, it was set on a press molding machine, and was heated and pressed under molding conditions of 170 ° C., 10 kg / cm ² , and 120 seconds to obtain a flat phenolic resin molded article having a thickness of 5.0 mm. I got (Evaluation of Performance) The specific gravity of the phenolic resin molded products obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was measured, and a bending test and a heat insulating test were performed. As shown in FIG. 4, in the bending test, a test piece (7) formed by cutting out the obtained phenolic resin molded article was spanned on a support table (8) (8) in an ASTM bending strength test method. 1
The test piece (7) was adjusted at a load speed of 50 mm / min.
As shown in FIG. 5, in the heat insulation test, the test piece (4) formed by cutting out the obtained phenolic resin molded body was placed at a position facing the far-infrared ray irradiator (6). The test was performed using an apparatus in which an iron plate (5) was inserted between the test piece (4) and the far infrared ray irradiator (6) in parallel with the test piece (4). That is, the far-infrared irradiator (6) emits far-infrared rays toward the iron plate (5) to heat the iron plate (5), and the test piece (4) heated by the radiant heat of the heated iron plate (5). ) Was measured on the surface (A) and the temperature on the back surface (B) on the iron plate side, respectively, and the temperature difference was evaluated. At this time,
When the temperature difference between the front surface (A) and the back surface (B) of the test piece (4) is large, heat is not easily transferred from the front surface (A) side to the back surface (B) side, and therefore, the heat insulating property is large. It can be evaluated. In the measurement, the temperature of the back surface (B) when the temperature of the front surface (A) of the test piece (4) was heated to 80 ° C. was measured, and the temperature difference at this time was evaluated.

The results of these measurements are shown in Table 1.

[0021]

[Table 1]

From Table 1, it can be seen that in Examples 1 to 3, the temperature difference between the heated front surface (A) and the back surface (B) in the heat insulation test was larger than that in Comparative Example 1, and the heat insulation was larger. It can be seen that the property has been improved. Comparing the other performances, Examples 1 and 2 are lighter than or equal to Comparative Example 1 in specific gravity, and equivalent or more in flexural strength and flexural modulus. And it can be seen that they have equal or higher strength. In Example 3, although the bending strength was slightly deteriorated as compared with Comparative Example 1, the flexural modulus was improved, the specific gravity was significantly reduced, and the heat insulating property was the highest among Examples. Has improved.

From the above results, it was found that Examples 1 to 3 were able to improve the heat insulating property while maintaining the same and higher strength and light weight as those of Comparative Example 1 or more.

[0024]

The phenolic resin laminate according to the first aspect of the present invention is characterized in that a phenolic resin containing a foaming agent is provided above and below a layer of a honeycomb sheet material (2) having cells (21) opened vertically. Since the SMC layer (1a) composed of the condensate and the chopped strands of glass fiber is formed, the phenolic resin molded product obtained by heating and pressing the phenolic resin laminate is the SMC layer (1a). ) And the above-mentioned layer of the honeycomb-shaped sheet material are integrated with the cells of the honeycomb-shaped sheet material containing air. That is, the phenolic resin precondensate constituting the layer (1a) of the SMC that has been heated and melted is placed in the cells (21) of the honeycomb sheet material (2) from the upper and lower openings of the cells (21). As it penetrates and hardens, the air in cell (21) loses its escape and is trapped in cell (21). Therefore, the phenolic resin molded article is lightweight, and the layer of the honeycomb-shaped sheet material (2) containing a large amount of air exhibits an excellent heat insulating effect. Further, in the phenolic resin molded article, the honeycomb sheet material (2) is composed of cells (2
1) has excellent strength because it is structurally open to the top and bottom and is robust against a load from the top and bottom.

The phenolic resin laminate according to claim 2 is
Since the longest distance of the diameter of the hole opened above and below the cell (21) of the honeycomb-shaped sheet material (2) is within a range of 3 to 30 mm, when the phenol resin laminate is heated and pressed, the weight is reduced. And a phenolic resin molded article having both excellent strength.

The phenolic resin laminate according to claim 3 is
Since the layers of the nonwoven fabric (3) are formed on the upper and lower surfaces of the layer (1a) of the SMC, a phenolic resin molded article having the nonwoven fabric (3) as a decorative surface can be obtained by one molding, The work of gluing the decorative surface later by gluing or the like can be omitted.

In the method for producing a phenolic resin molded product according to a fourth aspect, the phenolic resin laminate is heat-pressed, so that the obtained phenolic resin molded product is lightweight, has excellent strength, and has heat insulating properties. Is improved.

[Brief description of the drawings]

FIG. 1A is a cross-sectional view showing an example of a phenolic resin laminate of the present invention, and FIG. 1B is a cross-sectional view showing a phenolic resin molded article obtained by using the phenolic resin laminate shown in FIG. FIG.

FIG. 2 (c) is a cross-sectional view showing another example of the phenolic resin laminate of the present invention, and FIG. 2 (d) shows a phenolic resin molded article obtained by using the phenolic resin laminate shown in FIG. FIG.

FIG. 3 is a partially broken perspective view showing an example of the phenolic resin laminate of the present invention.

FIG. 4 is a side view showing a measuring method of a bending test in the example of the present invention.

FIG. 5 is a side view showing a measurement method of a heat insulation test in an example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 SMC 1a Layer of SMC 1b Layer of SMC 2 Honeycomb-like sheet material 21 Cell 3 Nonwoven fabric

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B29C 43/00-43/58

Claims (4)

(57) [Claims] 1. Paper having cells (21) opening up and down
A layer (1a) of SMC comprising a phenolic resin precondensate containing a foaming agent and a chopped strand of glass fiber is formed on and under a layer of a honeycomb-shaped sheet material (2) made of The SMC is obtained by spraying a chopped strand of glass fiber having a fiber length of 10 to 50 mm on a phenol resin composition mixed with a foaming agent. Laminate. 2. The phenolic resin laminate according to claim 1, wherein the longest distance of the diameter of the hole opened above and below the cell (21) of the honeycomb sheet material (2) is 3 to 30 mm. . 3. The phenolic resin laminate according to claim 1, wherein a nonwoven fabric layer is formed on upper and lower surfaces of the SMC layer. 4. A method for producing a phenolic resin molded product, comprising subjecting the phenolic resin laminate according to claim 1 to heat and pressure molding.