WO1997004938A1

WO1997004938A1 - Process for molding synthetic resins

Info

Publication number: WO1997004938A1
Application number: PCT/JP1996/002074
Authority: WO
Inventors: Hiroshi Kataoka; Yuo Umei; Iwao Katou
Original assignee: Asahi Kasei Kogyo Kabushiki Kaisha
Priority date: 1995-07-25
Filing date: 1996-07-24
Publication date: 1997-02-13
Also published as: CN1098763C; MY141391A; CN1195312A

Abstract

A process for molding a synthetic resin, characterized by conducting the molding (1) by the use of a main metal mold constituting a mold cavity covered with a heat insulating layer in a state closely adherent to the mold surface in which a heat insulating layer made of a heat-resistant polymer having a thickness of more than 0.1 mm but below 0.5 mm covers the mold surface, and a metal layer covers the heat insulating layer in a state closely adherent to the insulating layer, (2) under the conditions that the integral [(mold surface temp.)-(softening temp. of the synthetic resin)] value (ΔH) over the period in which the mold surface temperature equals or exceeds the softening temperature of the synthetic resin after the point of time when the resin to be molded has come into contact with the mold surface is 2 sec. °C or above, and/or that the integral [mold surface temp.-(softening temp. of the synthetic resin - 10 °C)] value (Δh) over the period in which the mold surface temperature equals or exceeds the softening temperature (°C) of the synthetic resin minus 10 after the above point of time is 5 sec. °C or above, and (3) under the condition that the mold surface temperature lowers to the softening temperature of the resin or below after 5 seconds from the point of time when the resin to be molded has come into contact with the mold surface.

Description

Description Molding method for synthetic resin

V

5 Technical fields

The present invention relates to a method for molding a synthetic resin. More specifically, the present invention provides a molding method suitable for synthetic resin injection molding, blow molding and the like. In recent years, there has been a growing demand to omit post-processing such as painting of synthetic resin injection molded products and blow molded products. In other words, there is a strong demand to eliminate painting in order to reduce manufacturing costs, recycle molded products, and reduce environmental destruction due to solvent evaporation during painting. In particular, there is a strong demand for the processing of synthetic resin housings for electrical equipment, electronic equipment, and office equipment to be omitted. The present invention provides a molding method that economically satisfies these requirements. Background art

15 Injecting thermoplastic resin into the mold cavity and molding it to improve the reproducibility of imparting the shape state of the mold surface to the molded product and improve the appearance of the molded product. It can be achieved to some extent by selecting molding conditions such as increasing the injection pressure and increasing the injection pressure. Similarly, in blow molding, in order to improve the appearance of the molded product, it is usually necessary to increase the resin temperature or the mold temperature, or to increase the blow gas pressure, etc.

You can achieve this to some extent by choosing 20.

The most significant of these factors is the mold temperature, and the higher the mold temperature, the better. However, when the mold temperature is increased, the cooling time required for cooling and solidifying the plasticized resin is increased, and the molding efficiency is reduced. Improves the reproducibility of the mold surface without increasing the mold temperature, and does not increase the required cooling time even if the mold temperature is increased

25 different methods are required.

A method of repeating heating and cooling of the mold by alternately supplying a heating medium and a cooling medium to the mold and attaching holes for heating and cooling to the mold is called Plastic Technology, June, p. 1 5 1 (1 9 This method consumes a large amount of heat and requires a long cooling time. A mold in which the mold wall is covered with a substance with low thermal conductivity, that is, a thin heat-insulating layer

Is disclosed in WO 93 06 980 and the like.

<Furthermore, the mold wall is covered with a thin heat-insulating layer, and the surface is further covered with a thin metal layer.

U SP 3 7 3 4 4 4 9, U SP 5 3 0 2 4 6 7 and U S

It is shown in each specification of P 5 3 8 8 0 3. However, these known documents do not

A molding method that sufficiently satisfies both surface reproducibility and molding cycle time has not been disclosed.

I

Conventionally, mold surface reproducibility during molding and molding cycle time work in opposite directions.

In other words, when the mold temperature is increased, the mold surface reproducibility improves, but the molding cycle

The limb becomes longer. When using a heat-insulating layer-coated mold,

In the heat-insulating layer-coated mold, the thicker the heat-insulating layer, the better the mold surface reproducibility

Force <, molding cycle time becomes longer, and thicker outermost metal layer

Possibility is reduced. Conventional surface reproducibility and molding cycle time are in an alternative relationship.

Thus, it is an object of the present invention to achieve both.

In order to achieve both mold surface reproducibility and molding cycle time, a mold coated with a heat insulating layer

When a polymer is used as the heat insulating layer, the heat insulating layer is generally damaged during use.

If a large amount of inorganic filler is added to the synthetic resin, the mold surface becomes more easily damaged.

You. Also, depending on the type of synthetic resin to be molded, it is difficult to release it from the mold during molding.

It may be difficult, and improvement is required. As an improvement method, the heat insulation layer surface

It is conceivable to coat a thin metal layer on the substrate.

The present invention forms a limited range of a metal layer on the outermost surface of a limited range of a heat-insulating layer-coated mold.

Using the coated mold, molding under limited molding conditions, mold surface reproducibility, molding cycle

Provide molding methods that meet the three requirements of mold time and mold durability.

There are various problems with molds in which a thin metal layer is coated on the surface of a heat insulating layer.

I found that there was a title. That is, the relationship between the thickness of the metal layer and the thickness of the heat insulating layer is inappropriate.

If this is the case, the mold surface reproducibility during molding will be poor.

The cycle time becomes longer and the molding efficiency decreases.

The required heat insulation layer thickness and metal layer thickness have a close relationship with the softening temperature of the synthetic resin to be molded, molding conditions such as mold temperature and resin temperature, etc. It must be firmly adhered, and the contact surface between the heat-insulating layer and the metal layer must withstand repeated cooling and heating cycles by molding the synthetic resin.The surface metal layer must have durability, especially molding It is necessary to solve problems such as a need for special durability when an inorganic filler is blended with the synthetic resin to be used. Disclosure of the invention

In order to solve these problems, the present inventors studied a mold coated with a heat insulating layer, and found that the heat insulating material covering the main mold surface and its thickness, its coating state, and the main mold material The relationship between the combination, the adhesion strength of the metal layer covering the outermost surface and its thickness, the softening temperature of the synthetic resin to be molded, the molding conditions of the synthetic resin, etc. is examined, and the mold surface reproducibility of the molded product, molding cycle The present invention satisfies the three requirements of thyme and mold durability.

That is, the present invention is as follows.

1. In the molding method of synthetic resin,

(1) On the surface of the mold that constitutes the mold cavity of the main mold made of metal, there is a heat insulating layer of less than 0.5 mm that exceeds 0.1111111 and that is made of a heat-resistant polymer adhered to the mold surface. Using a heat-insulating layer-coated mold in which a metal layer closely adhered to the heat-insulating layer is present,

(2) After the synthetic resin to be molded comes into contact with the mold surface, while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin, the integral value (ΔΗ) of the value of (mold surface temperature minus the plasticization temperature of the synthetic resin) is 2 Molding conditions of seconds * ° C or more, and / or while the mold surface temperature is (synthetic resin softening temperature-10 ° C) or more, (mold surface temperature-(softening temperature of synthetic resin-10 ° C) )} Molding conditions with integrated value (A h) of 10 seconds · ° C or more,

(3) A synthetic resin molding method in which molding is performed under molding conditions such that the mold surface temperature falls below the softening temperature of the synthetic resin 5 seconds after the synthetic resin to be molded contacts the mold surface.

2. In the injection molding method of synthetic resin,

(1) On the surface of the mold that constitutes the mold cavity of the main mold made of metal, there is a heat-insulating layer of less than 0.5 mm exceeding 0.1111111 made of a heat-resistant polymer adhered to the mold surface. Using a heat-insulating-layer-coated mold having a metal layer having a thickness of 1 to 3 mm or less on the heat-insulating layer and a thickness of 0.01 to 0.1 mm, (2) Molding conditions in which the main mold temperature is set to 15 ° C or more and 100 ° C or less, and set to a temperature not more than 20 ° C from the curing temperature of the synthetic resin, and

(3) After the synthetic resin to be molded comes into contact with the surface of the mold, the integral value (ΔΗ) of (the mold surface temperature minus the softening temperature of the synthetic resin) is 2 seconds while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin. · ° C or more molding conditions, and / or the mold surface temperature (synthetic resin钦化temperature one 1 0 ° C) softening temperature one 1 0 (mold surface temperature one (synthetic resin while in the above ^e C )} Molding conditions where the integrated value (mmh) is 10 seconds · ° C or more,

(4) A synthetic resin injection molding method in which molding is performed under molding conditions such that the mold surface temperature falls below the softening temperature of the synthetic resin 5 seconds after the molded resin contacts the mold surface.

3. In the injection molding method of synthetic resin,

(1) A heat insulating layer of more than 0.1 mm and less than 0.5 mm made of a heat-resistant polymer adhered to the mold surface is present on the mold surface constituting the mold cavity of the main mold made of metal, Further, on the heat insulating layer, the thickness of the metal layer of the convex portion is 1/3 or less of the thickness of the heat insulating layer, and is 0.01 to 0.1 mm, and the depth of the concave portion is 0.001. Using a heat-insulating layer-coated mold having a metal layer having a grain-like surface of about 0.09 mm and having a thickness smaller than the thickness of the convex portion,

(2) Molding conditions in which the main mold temperature is set to 15 ° C or higher, 100 ° C or lower, and a temperature equal to or lower than the softening temperature of the synthetic resin minus 20 ° C,

(3) After the synthetic resin to be molded comes into contact with the mold surface, while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin, the integral value (ΔΗ) of the value of (mold surface temperature-plasticization temperature of synthetic resin) is 2 Second

• Molding conditions of more than ° C, and / or while the mold surface temperature is (Synthetic resin tempering temperature-10 ° C) or more (Mold surface temperature-(Synthetic resin softening temperature-10 ° C) } Molding conditions with integrated value (A h) of 10 seconds · ° C or more,

4. When the thickness of the heat insulation layer is more than 0.1 mm and less than 0.4 mm, and the thickness of the metal layer is 1/3 or less of the thickness of the heat insulation layer, and it is 0.01 to 0.07 mm. Yes, integrated value (mH) is 2 seconds · ° C or more and 50 seconds or less, and Z or integrated value (Ah) is 10 seconds · ° C or more

100 seconds or less, and 5 seconds after the synthetic resin contacts the mold surface, the mold surface temperature 3. The injection molding method for a synthetic resin according to the above item 2, wherein the injection molding is performed under molding conditions in which the degree is lowered to (the softening temperature of the synthetic resin is 1 ° C. or less).

5. The thickness of the heat insulation layer is more than 0.12 mm and less than 0.3 mm, and the thickness of the metal layer is 1 Z5 or less of the heat insulation layer and 1100 or more, and 0.02 to 0. 0.6 mm and the integrated value (ΔH) is 5 seconds or more and 40 seconds or less, and / or the integrated value (Ah) is 12 seconds or more. The injection molding is performed under the molding conditions in which the mold surface temperature is decreased to (the softening temperature of the synthetic resin −10 ° C.) or less 5 seconds after the synthetic resin comes into contact with the mold surface. Injection molding of synthetic resin.

6. When the thickness of the heat insulation layer is more than 0.1 mm and less than 0.4 mm, and the thickness of the metal layer of the projection is 1 to 3 or less of the thickness of the heat insulation layer, and is 0.01 to 0.07 mm Yes, the depth of the grain-shaped recess is 0.005 to 0.06 mm, and the integral value (ΔH) is 2 seconds · ° C or more and 50 seconds · ^eC or less, and / or the integral value ( Δh) is at least 10 seconds · ° C and at most 100 seconds · ° C, and after 5 seconds from the contact of the synthetic resin with the mold surface, the mold surface temperature becomes (the curing temperature of the synthetic resin minus 10). ° C) The injection molding method for a synthetic resin according to the above item 3, wherein the injection molding is carried out under molding conditions reduced below.

7. The thickness of the heat-insulating layer is more than 0.12 and less than 0.3 mm, the thickness of the metal layer of the projection is 15 or less of the thickness of the heat-insulating layer, and 0.01 to 0.06 mm. And the depth of the grain-shaped concave portion is 0.005 to 0.04 mm, and the integral value (ΔH) is 5 seconds · ° C to 40 seconds · ° C or less, and / or the integral value (A h) is 12 seconds · ° C or more and 70 seconds · ° C or less, and 5 seconds after the synthetic resin comes into contact with the mold surface, the mold surface temperature becomes (curing temperature of synthetic resin-10 ° C 3.) The injection molding method for a synthetic resin according to the above item 3, wherein the injection molding is performed under the following molding conditions.

8. The injection molding method for a synthetic resin as described in 2, 3, 4, 5, 6, or 7 above, wherein the average flow velocity in the mold of the synthetic resin is 20 to 300 mm / sec.

9. In the blow molding method of synthetic resin,

(1) On the surface of the mold constituting the mold cavity of the main mold made of metal, there is a heat insulating layer of less than 0.5 mm, which exceeds 0.11111111 and which is made of a heat-resistant polymer adhered to the mold surface, and Using a heat-insulating layer-coated mold having a metal layer with a thickness of 13 to 13 mm or less of the heat-insulating layer and a thickness of 0.02 to 0.1 mm on the heat-insulating layer, (2) molding conditions in which the main mold temperature is set to 15 ° C or higher, 100 ° C or lower, and a temperature equal to or lower than the softening temperature of the synthetic resin minus 20.

(3) After the synthetic resin to be molded comes into contact with the mold surface, while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin, the integral value (ΔΗ) of the value of (mold surface temperature-softening temperature of the synthetic resin) is 1 0 seconds · ° C or more and 200 seconds · ° C or less, and Z or while the mold surface temperature is (synthetic resin softening temperature-10 ° C) or more (Mold surface temperature-(synthesis) The softening temperature of the resin is less than 10 ° C)} The molding conditions are such that the integrated value (Δΐι) is at least 20 seconds · at least 400 seconds · ° C.

(4) A blow molding method for synthetic resin in which molding is performed under molding conditions such that the mold surface temperature drops below the softening temperature of the synthetic resin 5 seconds after the synthetic resin to be molded contacts the mold surface.

1 0. The thickness of the heat insulation layer is 0.2 mm or more and less than 0.5 mm, and the thickness of the metal layer is 15 or less of the thickness of the heat insulation layer and 1 100 or more, and 0.04 to 0. 0.6 mm, integral value (ΔΗ) is 20 seconds · ° C or more and 100 seconds or less · ° C, and / or yield value (Δΐι) is 30 seconds · ° C or more and 300 seconds' ° C. The blow molding method for synthetic resin according to 9 above, wherein the blow molding is performed under molding conditions of not more than C.

1 1. In synthetic resin blow molding,

(1) A heat insulating layer of more than 0.1 mm and less than 0.5 mm made of a heat-resistant polymer adhered to the mold surface is present on the mold surface constituting the mold cavity of the main mold made of metal, Further, on the heat insulating layer, the metal layer thickness of the convex portion is not more than 1 Z 3 of the heat insulating layer thickness, and is 0.01 to 0.1 mm, and the depth of the concave portion is 0.005. Using a heat-insulating mold with a metal layer having a grain-like surface of ~ 0.09 mm,

(2) Molding conditions in which the main mold temperature is set to 15 ° C. or more, 100 ° C. or less, and a temperature not more than a temperature obtained by subtracting 20 ° C. from the aging temperature of the synthetic resin,

(3) After the synthetic resin to be molded comes into contact with the surface of the mold, while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin, the integral value (ΔΗ) of the value of (mold surface temperature-softening temperature of the synthetic resin) is 10 · ° C or more and 200 s or less °° C or less, and Z or while the mold surface temperature is (the synthetic resin's aging temperature-10 ° C) or more The temperature (10 ° C)) The integral value (Δh) of the value is 20 seconds · more than 400 seconds · ° C

(4) 5 seconds after the molded resin contacts the mold surface, the mold surface temperature becomes Blow molding method for molding a synthetic resin under molding conditions lowering below the softening temperature.

1 2. The thickness of the heat insulating layer is 0.2 mm or more and less than 0.5 mm, and the thickness of the metal layer of the projection is 15 or less of the thickness of the heat insulating layer, 1/100 or more, and 0.0 1 to 0. 0.8 mm, the depth of the grain-shaped recess is 0.05 to 0.07 mm, and the integral (ΔΗ) is 20 seconds or more and 100 seconds or less and ° C or less. The method for molding a synthetic resin according to 11 above, wherein blow molding is performed under molding conditions of 30 seconds or less and 300 seconds or less.

1 3. Perform blow molding under the molding conditions in which the time from when the parison contacts the mold surface until the blow pressure is sufficiently applied to the inner surface of the molded product is 1 to 5 seconds. Is a method for blow molding the synthetic resin described in 12.

1 4. The heat insulating layer and the metal layer are in close contact with each other at the fine irregularities interface, as described in 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 10, 11, 12 or 13. Molding method for synthetic resin.

1 5. The heat-resistant polymer forming the heat-insulating layer is composed of linear high molecular weight polyimide.

The method of molding a synthetic resin according to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 10, 11, 12, 13 or 14.

1 6. After forming the outermost surface layer of the heat insulating layer with a heat-resistant polymer containing 1 to 30% by weight of a fine powdered etching aid, the outermost layer of the heat insulating layer is subjected to chemical etching to obtain fine irregularities. The metal layer is formed by subjecting the surface to a chemical plating and, if necessary, performing one or more of a chemical plating and / or an electrolytic plating. The adhesion of the metal layer is 0.3. The above 1, using a mold coated with a metal layer of kg g 10 mm or more,

2, 3, 4, 5, 6, 7, 8, 9, 10, 10, 11, 12, 13, 14, 14 or 15;

1 7. Using a mold with a mirror surface on the metal layer surface or part of the metal layer surface 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 0, 1 1, 1 2 , 13, 14, 15, or 16.

1 8. Synthetic resin according to 1, 2, 4, 5, 8, 14, 15, or 16 above using a mold in which the metal layer surface or a part of the metal layer surface has a lens-like unevenness Molding method.

1 9. Using a mold in which the surface of the metal layer or a part of the surface of the metal layer is finely uneven and saturated. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 , 1 2, 1 3, 1 4. The method of molding a synthetic resin according to 4, 15 or 16.

20. The above 1, 3, 6, 7, 8, 11, 1, 1, 2, 1 using a mold in which one of the projections and depressions on the surface of the metal layer is specular and the other is severely erased. 3. The method for molding a synthetic resin according to 3, 14, 15, or 16.

2 1. The synthesis as described in 19 or 20 above, wherein a metal layer surface or a part of the metal layer surface uses a mold having a severely erased surface formed by multi-stage sand blasting and / or multi-stage etching. Resin molding method.

2 2. Use a metal layer whose metal layer is a metal layer having at least two layers, the hardness of the surface metal layer on the mold cavity side being lower than that of the inner metal layer, and the Z or etching property being large. 21. The method for molding a synthetic resin according to 21 above.

2 3. Mold of metal layer The etching rate of the metal layer on the cavity side is more than twice the etching rate of the inner metal layer, and a metal mold is used in which the above metal layer has a matte surface by multi-stage etching. 22. The method for molding a synthetic resin according to 22 above.

2 4. Synthetic resin to be molded is styrene-based resin such as polystyrene, rubber-reinforced polystyrene, styrene-acrylonitrile copolymer, ABS resin, styrene-methyl methacrylate copolymer. And 1, 2, 3, 4, 5, 6, 7, and 8 which are non-crystalline resins selected from methacrylic resins such as methacrylic resin, rubber reinforced polymethyl methacrylate, and the like, and polycarbonate. 8, 9, 10, 11, 12, 13, 13, 14, 15, 15, 16, 17, 18, 19, 20, 21, 22, 22, or 23 Fat molding method.

2 5. The synthetic resin is a synthetic resin containing 5 to 65% by weight of a fibrous or powdery inorganic filler, and the hardness of the metal layer on the outermost surface of the mold is such that the inorganic filler in the synthetic resin; W 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 0, 1, 1, 12, 1, 3, 1, 4, 1, 5, 1 6. The method for molding a synthetic resin described in 6, 17, 18, 19, 20, 20, 21, 22, 23 or 24.

26. The method for molding a synthetic resin according to the above item 25, wherein the synthetic resin is a synthetic resin containing more than 20% by weight and not more than 65% by weight of an inorganic filler.

27. The method for molding a synthetic resin according to the above item 25, wherein the synthetic resin is a synthetic resin containing 30 to 50% by weight of an inorganic filler. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a graph showing the temperature distribution change (calculated value) of the synthetic resin near the mold surface when the heated synthetic resin comes into contact with the steel main mold.

Figure 2 shows the synthetic resin and heat-resistant resin near the mold surface when the heated synthetic resin comes into contact with the mold in which 0.1 mm polyimide is coated on the mold surface of the steel main mold. FIG. 4 is a graph showing a change in the temperature distribution (calculated value) of FIG.

Figure 3 shows the synthetic resin and the heat-resistant resin near the mold surface when the heated synthetic resin comes into contact with the mold of 0.5 mm polyimide coated on the mold surface of the steel main mold. It is a graph figure which shows a temperature distribution change (calculated value).

Figure 4 is a graph showing the change over time (calculated value) of the mold surface temperature when a heated synthetic resin comes into contact with a mold in which various thicknesses of polyimide are coated on the mold surface of a steel main mold. FIG.

Fig. 5 shows the temperature of the mold surface when the synthetic resin was brought into contact with a mold in which a 0.2 mm thick polyimide was coated on the mold surface of a steel main mold at various resin temperatures and mold temperatures. It is a graph which shows a time-dependent change (calculated value).

Fig. 6 shows the mold surface when synthetic resin comes in contact with a mold in which 0.2 mm thick polyimide is coated on the mold surface of a steel main mold at various mold thicknesses and mold temperatures. FIG. 4 is a graph showing a change over time (calculated value) of temperature.

Fig. 7 shows the heated synthetic resin in a mold in which the mold surface of a steel main mold is coated with 0.3 mm of polyimide, and the surface is further coated with 0.2 mm of nickel. FIG. 4 is a graph showing a temperature change (calculated value) of a mold surface (an interface between a resin surface and a mold surface) when a contact occurs.

Figure 8 shows that the steel main mold was heated to a mold in which 0.3 mm of polyimide was coated on the mold surface and the surface was coated with a nickel layer of various thicknesses. FIG. 4 is a graph showing the change over time (calculated value) of the temperature of the mold surface (the interface between the resin surface and the mold surface) when the synthetic resin comes into contact with the synthetic resin.

Figure 9 shows synthetic resin: rubber reinforced polystyrene (HIPS :), molded product thickness: 2 mm, synthetic resin temperature: 240, main mold temperature: 50 ° C, nickel layer thickness: 0.0 3 mm to change the polyimide layer thickness to 0.1 mm, 0.2 mm, 0.3 mm, and 0.5 mm Graph (9-A) showing the change over time in the mold surface temperature when molding is performed in a plasticized state, and the graph (9-A) showing the relationship between the aging temperature of the synthetic resin and the mold surface temperature being higher than the softening temperature of the synthetic resin. FIG. 9 is a graph (9-1B) showing the relationship between the integrated value (calculated value) of the value of one synthetic resin (softening temperature).

Figure 10 shows synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240 ° C and 270 ° C, main mold temperature: 30 and nickel layer thickness: 0.05 The graph (10-A) shows the change over time in the mold surface temperature when molding with the thickness of the polyimide layer changed to 0.1 mm and 0.2 mm in mm. FIG. 11 is a graph (10—B) showing the relationship between the temperature and the integrated value (calculated value) of the value of (mold surface temperature-plastic resin softening temperature) while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin. .

Figure 1 1 is a synthetic resin: HIPS, moldings Thickness: 2 mm, the synthetic resin temperature: 2 4 0 ° C, the main mold temperature: 7 0 ^e C, nickel layer thickness: at 0. 0 3 mm, Porii A graph showing the change over time of the mold surface temperature (111 A) when the mold layer thickness was changed to 0.1 mm and 0.2 mm, and the aging temperature of the synthetic resin and the mold surface FIG. 11B is a graph (111B) showing a relationship between an integral value (calculated value) of (mold surface temperature-synthetic resin tempering temperature) while the temperature is equal to or higher than the softening temperature of the synthetic resin.

Figure 12 shows synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240, main mold temperature: 50 ° C, nickel layer thickness: 0.01 mm, 0.0 A graph (12-A) showing the change over time of the mold surface temperature when molding with a polyimide layer thickness of 0.2 mm and 0.3 mm at 2 mm, and a synthetic resin Graph showing the relationship between the aging temperature of the mold and the integral value (calculated value) of the (mold surface temperature-synthetic resin aging temperature) value while the mold surface temperature is equal to or higher than the aging temperature of the synthetic resin. B).

Figure 13 shows that synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240 ° C, main mold temperature: 50 ° C, polyimide layer thickness: 0.3 mm, Graph showing the time-dependent change of the mold surface temperature when the thickness of the nickel layer is changed to 0.01 mm, 0.02 mm, 0.03 mm, 0.05 mm, and 0.1 mm. Relationship between the figure (13-A) and the integrated value (calculated value) of the value (mold surface temperature-synthetic resin softening temperature) while the softening temperature of the synthetic resin and the mold surface temperature are higher than the softening temperature of the synthetic resin. Fig. 13 is a graph (13-B). Figure 14 shows that synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240 ° C, main mold temperature: 50 ° C, polyimide layer thickness: 0.2 mm, A graph (14-A) showing the change over time of the mold surface temperature when molding with the thickness of the nickel layer changed to 0.02 mm and 0.03 mm. 0.05 m, and synthetic resin Graph showing the relationship between the mold temperature and the integral value (calculated value) of the (mold surface temperature-synthetic resin softening temperature) value while the mold surface temperature is above the softening temperature of the synthetic resin. ).

Fig. 15 shows that synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240 ° C, main mold temperature: 30 ° C, polyimide layer thickness: 0.2 mm, A graph (15-A) showing the change over time of the mold surface temperature when molding with the thickness of the nickel layer changed to 0.01 mm. 0.02 mm and 0.03 mm; Graph diagram showing the relationship between the resin softening temperature and the integral value (calculated value) of the (mold surface temperature-synthetic resin softening temperature) value while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin (15 — B ).

Fig. 16 shows that synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240 ° C, nickel layer thickness: 0.01 mm, polyimide layer thickness 0.1 mm, A graph (16-A) showing the change over time in the mold surface temperature when the main mold temperature was changed to 30 ° C, 40 ° C, and 50 ° C, and the temperature of the synthetic resin Fig. 16 (B) shows the relationship between the mold temperature and the integral value (calculated value) of the (mold surface temperature-synthetic resin softening temperature) value while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin. is there.

Fig. 17 shows synthetic resin: HIPS, molded product thickness: 2 mm, synthetic resin temperature: 240 ° C, nickel layer thickness: 0.02 mm, polyimide layer thickness 0.1 mm, A graph (17—A) showing the change over time of the mold surface temperature when the mold temperature was changed to 30 ° C, 40 ° C, 50 ° C, and 70 ° C. A graph showing the relationship between the plasticization temperature of the synthetic resin and the integrated value (calculated value) of the (mold surface temperature-plasticization temperature) while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin. 1 7 — B).

Fig. 18 shows that synthetic resin: HIPS, molded product thickness: 2 mm, main mold temperature: 30 ° C, nickel layer thickness: 0.01 mm, polyimide layer thickness: 0.1 mm, A graph (18-A) showing the change over time in the mold surface temperature when molding with the synthetic resin temperature changed to 210, 240 ° C, and 270 ° C, and the softening of the synthetic resin Integration of the value of (mold surface temperature-plastic resin softening temperature) while the temperature and mold surface temperature are above the softening temperature of the synthetic resin Fig. 18 is a graph (18-B) showing the relationship with the values (calculated values).

Fig. 19 shows synthetic resin: HIPS, molded product thickness: 2 mm, main mold temperature: 3 (TC, polyimide layer thickness: 0.1 mm, nickel layer thickness: 0.02 mm, synthetic) in the case of molding a resin temperature 2 1 0 ° C, 2 4 0 ° C, 2 7 0 e C to alter a graph showing the time course of the mold surface temperature - and (1 9 a), a synthetic resin Graph showing the relationship between the mold softening temperature and the integrated value (calculated value) of the (mold surface temperature-synthetic resin softening temperature) value while the mold surface temperature is equal to or higher than the plasticization temperature of the synthetic resin (1 9 — B ).

Fig. 20 shows that synthetic resin: HIPS, molded product thickness: 2 mm, main mold temperature: 30 ° C, polyimide layer thickness: 0.2 mm, and nickel layer thickness: 0.01 mm. , Synthetic resin temperature: 210 ° C, 240 ° C, 27 (Temperature change of mold surface temperature when molding by changing to TC (20-A), and synthetic resin Graph showing the relationship between the softening temperature of the mold and the integral value (calculated value) of the (mold surface temperature-synthetic resin tempering temperature) value while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin (20-B) It is.

Fig. 21 shows synthetic resin: HIPS, molded product thickness: 2 mm, main mold temperature: 30 ° C, polyimide layer thickness: 0.2 mm, nickel layer thickness: 0.02 mm. A graph (2 1 — A) showing the change over time of the mold surface temperature when molding was performed by changing the temperature of the synthetic resin to 210 ° C, 240 ° C, and 270 ° C; Graph showing the relationship between the curing temperature of the mold and the integral value (calculated value) of the (mold surface temperature-synthetic resin softening temperature) value while the mold surface temperature is equal to or higher than the plasticization temperature of the synthetic resin (2 1 — B ).

Figure 22 shows the synthetic resin: HIPS, the synthetic resin temperature: 240 ° C, the main mold temperature: 50, the polyimide layer thickness: 0.2 mm, and the nickel layer thickness: 0.02. Figure 2 (A) shows the change over time in the mold surface temperature when molding was performed with the molded product thickness changed to 3 mm, 4 mm, and 5 mm in mm, and the softening temperature of the synthetic resin and the mold. FIG. 9 is a graph (22-B) showing the relationship between the (mold surface temperature-synthetic resin softening temperature) value and the integrated value (calculated value) while the surface temperature is equal to or higher than the softening temperature of the synthetic resin.

Figure 23 shows synthetic resin: polyoxymethylene (POM), molded product thickness: 2 mm, synthetic resin temperature: 200 ° C, main mold temperature: 60 ° C, polyimide layer thickness: 0 Graph showing the change over time of the mold surface temperature when molding was performed with the Nigger layer thickness changed to 0.01 mm, 0.02 mm, and 0.04 mm at 2 mm. ) And the synthetic tree Graph showing the relationship between the softening temperature of the fat and the integral value (calculated value) of the (mold surface temperature-synthetic resin curing temperature) value while the mold surface temperature is equal to or higher than the curing temperature of the synthetic resin (23- B).

Figure 24 shows the synthetic resin: POM, molded product thickness: 2 mm, synthetic resin temperature: 200 ° C, main mold temperature: 60 ° C, nickel layer thickness of 0.02 mm, and Polyimi Graph (24-A) showing the change over time in the mold surface temperature when molding was performed while changing the mold thickness to 0.2 mm. 0.3 mm and 0.4 mm, and the softening temperature of the synthetic resin. FIG. 11 is a graph (24-B) showing the relationship between the mold surface temperature and the integral (calculated value) of the (mold surface temperature-synthetic resin softening temperature) value while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin.

Fig. 25 shows synthetic resin: HIPS, molded product thickness: 3 mm, heat insulating material: epoxy resin, heat insulating layer thickness: 0.3 mm, metal layer thickness: 0.03 mm, resin temperature: 200 ° C the main mold temperature: and when molded at 4 0 ° C, the synthetic resin: HIPS, moldings thickness: 2 mm, insulation material: sera mission-box _{_{(Y 2 0 3 Z r 0}} 2), the heat insulating layer thickness: 0. 3 mm, the metal layer is no, resin temperature: indicated by 2 4 0, in the case of forming the form with varying main mold temperature ^{3 5 ° C, 5 0 e} C, the aging of the mold surface temperature The graph (25-A) shows the integrated value of (mold surface temperature-synthetic resin aging temperature) while the aging temperature of the synthetic resin and the surface temperature of the mold are higher than the aging temperature of the synthetic resin. (25-B).

Figure 26 shows synthetic resin: HIPS, molded product thickness: 2 mm, polyimide thickness: 0.5 mm, nickel thickness: 0.03 mm, synthetic resin temperatures: 240 ° C and 270 ° C, Main mold temperature: A graph (26-A) showing the change over time of the mold surface temperature when molding at 50 ° C and 70 ° C. The softening temperature of the synthetic resin and the mold surface temperature Fig. 26 is a graph (26-B) showing the relationship between the (mold surface temperature-synthetic resin softening temperature) value and the integrated value (calculated value) while the temperature is above the softening temperature of the synthetic resin.

FIG. 27 is a diagram showing a change in the mold surface temperature shown in FIG. 6 of the known document U.S. Pat. No. 5,388,803 of the reference and a change in the mold surface temperature of the present invention.

FIG. 28 is a graph showing the temperature change of the thermal conductivity of the resin used to calculate the change in the mold surface temperature in each figure shown in the present invention.

FIG. 29 shows the ratio of the resin used in calculating the mold surface temperature change in each figure shown in the present invention. It is a graph which shows the temperature change of heat.

FIG. 30 is a graph showing the heat generated by shearing in the mold during injection molding.

FIG. 31 is a graph showing a change in glossiness of an HIPS injection molded product depending on a resin temperature when a general mold having no heat insulating layer and a mold having a heat insulating layer are used.

Figure 32 shows the integration of the value of (mold surface temperature-synthetic resin aging temperature) while the gloss of the HIPS injection-molded product with the heat-insulating layer-coated mold and the mold surface temperature are higher than the aging temperature of the synthetic resin. It is a graph which shows the relationship with a value ((DELTA) *).

Fig. 33 shows the gloss of the HIPS injection-molded product using the heat-insulating layer-coated mold and the {mold surface temperature-(synthetic resin temperature-10 ° C) while the mold surface temperature is higher than (softening temperature of synthetic resin-10 ° C). FIG. 4 is a graph showing a relationship between a resin softening temperature and an integral value (Δΐι). Fig. 34 is a graph showing the relationship between mold temperature and gloss of molded products when HIPS (Stylon 495, trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) is injection-molded with a general metal mold. .

FIG. 35 is a cross section of the mold surface layer showing that the heat insulating layer and the metal layer of the present invention are in close contact with each other at the fine uneven interface.

FIG. 36 is a partial cross-sectional explanatory view showing a state where a conventional Fresnel lens mold is injection-molded under ordinary molding conditions.

FIG. 37 is a partial sectional view of a Fresnel lens mold used in the method of the present invention. FIG. 38 shows a cross section of an erase-shaped molded article injection-molded by the method of the present invention and a cross-section of a mat-shaped molded article injection-molded with a conventional mold.

FIG. 39 is a diagram showing an injection-molded product used for describing the present invention.

FIG. 40 is a graph showing the change with time of the resin pressure applied to the mold wall surface during injection molding.

FIG. 41 is an explanatory view modelly showing how the injection-molded synthetic resin is filled into the fine irregularities on the mold surface.

FIG. 42 shows a sectional view of a mold for molding the molded article of the present invention.

FIG. 43 shows each step of etching the mold surface.

FIG. 44 shows each step of performing multi-stage etching on the mold surface.

FIG. 45 shows each step of performing multi-stage etching on the mold surface. FIG. 46 is a graph showing a surface unevenness pattern of a molded article in Example 10.

FIG. 47 is a graph showing the surface unevenness patterns of the mold and the molded product in Comparative Example 9. BEST MODE FOR CARRYING OUT THE INVENTION

The synthetic resin molded by the molding method of the present invention is a thermoplastic resin that can be used for general injection molding and blow molding, and is a polyolefin such as polyethylene and polypropylene, polystyrene, styrene and acrylonitrile. Polymers, rubber-reinforced polystyrene, styrene-methyl methacrylate copolymer, styrene resins such as ABS resin, polymethyl methacrylate, methyl methacrylate, styrene copolymer, etc. Resin, polyamide, polyester, polycarbonate, and vinyl chloride resin.

The molding method of the present invention can be particularly preferably used for polystyrene, rubber-reinforced polystyrene, styrene-acrylonitrile copolymer, ABS resin, styrene-methylmethacrylate copolymer and the like. Non-crystalline resin selected from methacrylic resin such as styrene resin, polymethylmethacrylate, rubber reinforced polymethylmethacrylate, and polycarbonate, and various fillers. It is the resin which was done. Various synthetic resins containing 5 to 65% by weight of an inorganic filler such as glass fiber, carbon fiber, whisker and other fibers, calcium carbonate, titanium oxide, and talc are particularly preferred in the present invention. It can be used properly. When a synthetic resin containing 5 to 65% by weight of an inorganic filler such as glass fiber or whisker is used for injection molding with a heat-insulating layer-coated mold, the surface of the mold is easily damaged by the inorganic filler. In particular, if the amount of the inorganic filler is more than 20% by weight, the heat insulation is easily damaged, and if the amount of the filler is more than 30% by weight, the mold surface is extremely easily damaged. In the present invention, the presence of a metal layer having a hardness equal to or higher than that of the inorganic filler on the mold surface and an appropriate thickness can prevent damage. In addition, polyamide resins, resins containing a large amount of acrylonitrile, and the like generally have poor releasability from a heat insulating layer having a polar group. In such a case, a metal layer is present on the surface of the heat insulating layer. By doing so, the releasability can be improved. The molding method of the present invention is most preferably used for rubber-reinforced polystyrene having a glass transition temperature of 80 to 120, containing 1 to 10% by weight of rubber.

Good molded articles molded by the molding method of the present invention are generally used synthetic resin injection molded articles such as housings for light electric equipment, electronic equipment, office equipment, various automobile parts, various daily necessities, and various industrial parts. Particularly preferred are housings for electronic equipment, electrical equipment, and office equipment, which are injection-molded at a multipoint gate, resulting in a large number of well lines. In addition, injection molding of good eraser-like molded products, good patterned grain molded products, good lenticular lenses molded using transparent synthetic resin, Fresnel lenses, etc., good high transmission, high diffusion plates, etc. Goods are also obtained. These molded products molded by the method of the present invention have good reproducibility of the mold surface, less noticeable weld lines, reproducibility of sharp edges on the mold surface, and reproducibility of minute irregularities on the mold surface. Thus, the above-mentioned various molded products can be obtained satisfactorily. These injection molded products are molded by a general injection molding method.In particular, the synthetic resin is molded during molding such as gas assist injection molding, liquid assist injection molding, oligomer assist injection molding, and injection compression molding. The effect is great when used in combination with low-pressure injection molding, in which the pressure against the wall surface is low, and / or the flow velocity of the synthetic resin in the mold is slow, and can be used favorably in the present invention.

Further, good molded products molded by the method of the present invention are various blow molded products requiring appearance.

The main mold composed of the metal described in the present invention includes iron or steel mainly composed of iron, alloy mainly composed of aluminum or aluminum, zinc alloy such as ZAS, beryllium copper alloy, etc. And metal molds generally used for molding synthetic resins. In particular, molds made of steel such as S55C and S45C can be used favorably. It is preferable that the mold surface in contact with the heat insulating layer of the main mold made of these metals is coated with hard chromium, nickel, or the like.

The heat-resistant polymer favorably used as the heat-insulating layer in the present invention is a polymer having a softening temperature higher than that of the synthetic resin to be molded, and preferably has a glass transition temperature of 140 ° C. or higher, more preferably. Or more preferably at least 160 ° C, most preferably at least 190 ° C, and / or a melting point of at least 200 ° C, more preferably at least 250 ° C. is there. Particularly preferably, it has a higher curing temperature than the molding temperature of the synthetic resin to be molded. Polymer. The thermal conductivity of the heat-resistant polymer is generally 0.001 to 0.003 calZcm 'sec'-C, which is much smaller than that of metal. Further, a polymer having a toughness of 4% or more, preferably 5% or more, more preferably 10% or more of the heat-resistant polymer is preferred. The elongation at break is measured according to ASTMD 638, and the tensile speed at the time of measurement is 5 mm / min.

The heat-resistant polymer that can be favorably used as the heat-insulating layer in the present invention is a heat-resistant polymer having an aromatic ring in the main chain, such as various amorphous heat-resistant polymers dissolved in an organic solvent, And various polyimides can be used favorably. Examples of the non-crystalline heat-resistant polymer include polysulfone and polyethersulfone. These amorphous heat-resistant polymers can be used as the heat insulating layer of the present invention by lowering the coefficient of thermal expansion by blending fillers such as carbon fibers and various inorganic fillers. As the polyimide, various types of polyimides, linear high molecular weight polyimides, and partially crosslinked polyimides can be used favorably. The linear high molecular weight polyimide has a large breaking elongation, is tough, has excellent durability, and can be used particularly favorably. The linear high molecular weight polyimide also includes polyamide imide and polyether imide.

Furthermore, in the present invention, an epoxy resin cured product having a small coefficient of thermal expansion, that is, an epoxy resin cured product obtained by combining a curing agent having a small thermal expansion coefficient with an epoxy resin, or an epoxy resin prepared by mixing various fillers in an appropriate amount A cured product can also be used (hereinafter, a cured epoxy resin is abbreviated as an epoxy resin). Epoxy resins generally have a large thermal expansion coefficient, and have a large difference in thermal expansion coefficient from metal molds. However, powders and particles such as glass, silica, talc, cres, zirconium silicate, lithium silicate, carbonic acid ruthenium, alumina, myrium, etc., which have a small coefficient of thermal expansion, glass fiber, whiskers, and carbon fiber An epoxy resin blended with a filler in which an appropriate amount such as that described above is blended with the epoxy resin to reduce the difference in thermal expansion coefficient from the metal mold can be used favorably as the heat insulating layer of the present invention.

In addition, epoxy resin or filler-containing epoxy resin, tough thermoplastic resin such as nylon, and various compounds that provide toughness such as rubber by adding toughness can be used favorably. . In particular, a polymer alloy cured by mixing polyether sulfone or polyether imide with an epoxy resin has excellent toughness and can be used favorably. The heat-insulating polymer forming the heat-insulating layer of the present invention is blended with fine powders such as titanium oxide, alumina, and calcium carbonate in order to improve the adhesion of the metal layer such as the plating formed on the heat-insulating layer. It is preferable. This fine powder may be blended in the entire heat insulating layer or only in the surface layer. If the amount of these fine powders is too large, the thermal conductivity of the heat insulating layer is reduced, making it difficult to achieve the object of the present invention. Generally, the fine powders are mixed in the range of 1 to 30% by weight.

In injection molding, blow molding, etc., the mold surface that comes into contact with the heated resin to be molded is subjected to severe cooling and heating cycles for each molding. In the prior art, the metal layer formed on the surface of the heat-insulating layer by plating or the like generally has a lower coefficient of thermal expansion than the heat-insulating layer made of a polymer. , Stress is repeatedly generated at each molding, and separation occurs at the interface. By reducing the difference between the coefficient of thermal expansion of the main mold and / or metal layer in contact with the heat insulating layer and the coefficient of thermal expansion of the heat insulating layer, the stress that causes separation can be reduced. In the present invention, the difference in the thermal expansion coefficients of the main mold and Z or metal layer thermal expansion coefficient and the heat insulating layer in contact with the heat-insulating layer is laid preferred is ^{4 X 1 0 _ 5 Z °} C below der Rukoto, more preferably is less than ^{3 X 1 0- 5 Z ° C} . In general, metals have a smaller coefficient of thermal expansion than polymers, and therefore, it is preferable to select a heat-resistant polymer having a smaller coefficient of thermal expansion. The coefficient of thermal expansion described here is the coefficient of linear expansion. The coefficient of thermal expansion of the heat insulating layer is the coefficient of linear expansion of the heat insulating layer in the plane direction.It is measured by the method shown in JISK 7197-1991, and it is measured between 50 ° C and 250 ° C. In the case where the glass transition temperature of the heat insulating layer is 250 ° C. or less, the average value is shown between 50 ° C. and the glass transition temperature. That is, a heat insulating layer is formed on a flat metal plate, and then the heat insulating layer is separated, and the heat insulating layer is heated to a temperature between 50 ° C. and 250 ° C. or 50 ° C. and a glass transition temperature. The average coefficient of thermal expansion during the measurement is measured.

The cause of separation between the heat insulating layer and the main mold or between the heat insulating layer and the metal layer is not only the difference in thermal expansion coefficient. However, the difference in the coefficient of thermal expansion is an extremely large factor. If the thermal insulation layer has a large adhesion between the main mold and / or metal layer, the thermal elastic layer has a low tensile modulus and a high elongation at break. Separation does not occur even if the difference between the coefficients is slightly large. However, a material suitable for the heat insulation layer, that is, high heat resistance, high hardness, and a mirror surface that is easily polished are satisfied. The heat insulating material is generally a heat-resistant hard synthetic resin having an aromatic ring in a main chain having a large elastic modulus. The heat-resistant hard synthetic resin layer is closely adhered to a main mold and / or a metal layer so that separation does not occur. To achieve this, it is preferable that the difference between the coefficients of thermal expansion be small.

Table 1 shows the metal of the main mold and the metal of the metal layer coated on the outermost surface that can be favorably used in the present invention. The thermal expansion coefficient of the heat-resistant polymer of the heat insulating layer and the general synthetic resin are shown in Table 1.

Table 1 Materials Thermal expansion coefficient

Steel 1.1 x 10-Z. C

main

Aluminum 2.2 "

Money

Aluminum alloy 2.4 "

Type

Copper 1.7 "

Passing

Brass 1.9 "

And

Zinc 3.3 "

Money

Zinc alloy (ZA S) 2.8〃

Genus

Tin 2.0 〃

Layer

Chrome 0.8 〃

Nickel 1.3 "Low thermal expansion type polyimide 0.4 ~ 3 dia. —General polyimide 3 ~ 6"

Polybenzimidazole 2.3 〃 heat Polyamide 3 ~ 7 "

Polyethersulfone 4-5.5 "layer Polysulfone 4-5.6"

Polyetherimide 4 to 5.6 "Polypropylene resin 6 to 9" Polystyrene resin 3 to 12 "

Composition Polyester resin 5 ~ 10 〃

Tree Epoxy resin 6 ~ 10 〃

Fat Nail resin 8 ~ 13 "

Polyethylene resin 8 to 18 〃 When the thermal expansion coefficient of the main mold and the metal layer or the metal layer is increased, a heat insulating layer having a relatively large thermal expansion coefficient can be used. Steel is the most commonly used mold material, but recently aluminum alloys and zinc alloys such as ZAS have come to be used. In the present invention, the closer the coefficient of thermal expansion is, the more preferable.If steel is used for the main mold, a low thermal expansion type polyimide having an extremely small coefficient of thermal expansion can be used satisfactorily. The structure (repeating unit) and glass transition temperature (T g) of the heat-resistant polymer that can be used well are shown. Table 2

In injection molding and blow molding, there is economic value in that a molded product with a complicated shape can be obtained in one molding. In order to coat the complex mold surface with a heat-resistant polymer and to make it adhere tightly, apply a heat-resistant polymer solution and a solution of Z or a heat-resistant polymer precursor, and then heat to obtain a heat-resistant polymer. Preference is given to a method of forming a united heat insulating layer or a method of vapor-depositing and polymerizing a heat-resistant polymer on the surface of a mold. In order to form a heat-resistant polymer by coating, it is preferable that the heat-resistant polymer or a precursor of the heat-resistant polymer can be dissolved in a solvent. A method in which a solution of a polyamic acid, which is a precursor of polyimide, is applied to a mold wall surface and then cured by heating to form polyimide on the mold wall surface can be used favorably. The reaction formula for forming polyimide from polyamic acid is shown below.

When a polyimide acid solution of a polyimide precursor is applied to the mold wall surface and then cured by heating to form a polyimide, the polyimide is heated at a heating cure temperature and Z or a heating cure atmosphere. Have different glass transition temperatures and thermal expansion coefficients. Generally, the higher the heating cure temperature, the higher the glass transition temperature and the lower the coefficient of thermal expansion. Generally, when the temperature of the polyamic acid is raised to 250 ° C or higher, almost all imidization proceeds <100% and polyimide is formed, but the movement of molecules after the formation of the polyimide becomes heat. It is thought to have an effect on the expansion coefficient. The heat insulating layer and the main mold of the present invention and / or the heat insulating layer and the metal layer are in close contact with each other. It is preferable that the adhesion is large. The heat-insulating layer closely adhered to the main mold or the metal layer closely adhered to the heat-insulating layer described in the present invention is not separated by a cooling and heating cycle caused by molding of synthetic resin more than 10,000 times. is there. The adhesion is preferably 0.3 kg Z 10 mm width or more at 23 ° C, more preferably 0.5 kg 10 mm width or more, and most preferably 0.7 kg Z l O mm width or more. It is. This is the separation force when the adhered metal layer or the metal layer and the heat insulation layer are cut to a width of 10 mm and pulled at a speed of 20 mm Z in a direction perpendicular to the bonding surface. Although there is considerable variation in this separation force depending on the measurement location and the number of measurements, it is important that the minimum value is large, and it is preferable that the adhesion force be stable and large. The adhesion described in the present invention is the minimum value of the adhesion of the main part of the mold. In order to improve the adhesion between the main mold and the heat insulating layer, the surface of the main mold can be formed into fine irregularities, the surface of the main mold can be variously plated, and primer treatment can be appropriately performed. As a preferable example of the primer treatment, polyimide containing a large amount of CO group or SO ₂ group easily adheres to the metal surface, and a thin layer of polyimide having excellent adhesion is used as the primer layer. The method of coating a general polyimide on this can be used favorably.

It is preferable that the adhesion between the heat insulating layer and the metal layer is also large, and it is preferable that both are in close contact with each other at the fine uneven surface interface. That is, it is preferable that the heat insulating layer and the metal layer alternately enter each other at the interface, so that the adhesion is increased by the anchor effect. The size of the fine irregularities at the interface between the heat insulating layer and the metal layer is such that the distance between the alternating irregularities is about 0.5 to 10 μm, and a part of the irregularities enters the complex and anchors. Irregularities that work well are preferred. The degree of fine irregularities is measured by observing the cross section of the interface between the heat insulating layer and the metal layer with a microscope. The preferred degree of fine unevenness is a reference length of 80 m, which is the average of the height of the top five peaks and the mean of the deepest valley bottom at the interface between the metal layer and the heat insulating layer. The difference is 0.5-10 / m. Since the irregularities described here are intricately and alternately complicated and the anchor effect works, and are not simple irregularities, the altitude should be set to the position where each irregularity is deepest.

The biggest advantage of injection molding and blow molding is that a mold with a complicated shape can be formed in one shot, and therefore, mold cavities generally have complex shapes. Power, power, It is extremely difficult to apply a coating substance to the surface of the mold cavity having such a complicated shape in a mirror-like manner. Therefore, the applied coating layer is polished later, or the coating layer is subjected to a numerical control milling machine. The best method is to grind the surface with a machine tool and then polish the surface to a mirror finish.

In the present invention, the total thickness of the heat insulating layer is selected within a range that satisfies the integral value and the change in mold surface temperature specified in the present invention, and is selected within an extremely narrow range of more than 0.1 mm and less than 0.5 mm. You. In injection molding, more preferably, more than 0.1 mm and less than 0.4 mm, particularly preferably, more than 0.1 mm and less than 0.3 mm, and in blow molding, preferably 0 mm 2 mm or more and less than 0.5 mm, more preferably 0.3 mm or more and less than 0.5 mm. With a thin heat-insulating layer of 0.1 mm or less, sufficient appearance improvement effect cannot be obtained. If the thickness of the heat insulating layer is too large, the required cooling time in the mold during molding becomes long, which is not preferable from an economic viewpoint.

In molding thermoplastics, mold temperature and molding cycle time are closely related. That is, the relationship between the mold temperature (T d) and the required cooling time in the mold (0) during molding is theoretically expressed by the following equation.

^{Θ = - (D 2/2} π a) · I n [(π / i) {(Τ χ - Τ d) /

(Τ c Τ Τ d)}]

θ: Cooling time (sec)

D: Maximum thickness of molded product (cm)

T c: Heated resin temperature during molding (° C)

T X: Softening temperature of molded product (° C)

a: Thermal diffusivity of resin

T d: Mold temperature (in)

The cooling time (0) is proportional to the square of the part thickness (D) and is a function of (T x-T d) Z (T c -Τ d).

Coating the main mold with a heat-insulating layer works in the same way as increasing the thickness of the molded product and increasing the cooling time, but on the other hand, decreasing the mold temperature reduces the cooling time. Work in the direction. It is economically preferable that the thickness of the heat insulating layer is thin and the appearance can be improved from the viewpoint of the molding cycle time. In the present invention, particularly preferably, the thickness of the heat insulating layer is set to the above-mentioned narrow range. Setting within this range will improve the appearance and improve the molding cycle time.

Many of the known documents in which a mold is coated with a heat insulating layer and a metal layer have a large heat insulating layer thickness. As the thickness of the heat-insulating layer increases, the mold surface reproducibility improves, but at the expense of molding cycle time, which greatly affects productivity and economy.

The relationship between the thickness of the heat insulating layer and the molding cycle time will be described with specific numerical values. When comparing the cooling time required for injection molding a 2 mm thick molded product using two types of molds with a heat insulation layer of 0.6 mm and 0.2 mm, synthetic resin injected And the thermal conductivity of the insulation material are generally almost the same level, so the ratio of the required cooling time in the mold is almost the same as the ratio of the cooling time required to form a 2.6 mm thick and 2.2 mm thick molded product. Be equivalent. 2. 6 mm thick and 2. cooling time required for molding 2 mm thick ratio, as shown in the formula, 2. become 6 ² / 2.2 ² = 1.4. The difference of 1.4 times in the required cooling time is an extremely large difference from the economical point of view of industrially molding synthetic resins. The preferred metal used for the metal layer coated on the surface of the heat insulating layer of the mold used in the present invention is a metal generally used for plating, and one or more of chromium, nickel, copper, and the like. It is. Suitable for use are chemical nickel plating, electrolytic nickel plating, chemical copper plating, electrolytic copper plating, and electrolytic chrome plating. The metal layer is coated on the surface of the heat insulating layer. The heat insulation layer and the metal layer must be in close contact with each other, and the adhesion is preferably at least 0.3 k10 mm, more preferably at least 0.5 kg10 mm, and most preferably. Is 0.7 kg / 10 mm or more. It is particularly preferred that the layer directly in contact with the thermal insulation layer be a chemical mech layer.

The surface of the metal layer may be any of a mirror surface, a matte surface with a fine uneven surface, a lens shape with a fine lens uneven surface, and a grain shape such as a grain of grain or a grain of wood, etc., and is selected as necessary. . The grain-shaped reliefs that can be favorably used in the present invention are patterned grain such as bark grain, grain grain, and hairline grain. In order to make the grain-shaped surface stand out, it is preferable to make one of the irregularities on the grain-shaped mold surface a mirror surface and the other a matte surface. In addition, when the unevenness of the grain-shaped surface is appropriately reduced and one of the unevenness is made to be a mirror surface and the other is erased, a so-called metallic appearance formed by a synthetic resin mixed with aluminum flakes or the like is obtained. And this is also included in the present invention.

Lenticular is a flat plate such as a fine Fresnel lens or a fine lenticular lens. Lens. In the case of a fine lens-shaped mold, when the heat insulating layer has a substantially constant thickness and the metal layer has a lens-shaped thickness variation, the thickness of the thin portion of the metal layer is defined as the metal layer thickness described in the present invention. When the thickness of the heat insulating layer is substantially constant and there is a lens-shaped thickness variation, the thickness of the thin portion of the heat insulating layer is defined as the heat insulating layer thickness described in the present invention.

The thickness of the heat insulating layer and the preferred thickness of the metal layer differ depending on whether the surface of the mold is mirror-like, matte-like, or grain-like, and the molding method differs depending on whether injection molding or blow molding is used. The preferred thickness of the heat insulating layer and the preferred thickness of the metal layer in each molding method are described in detail below.

In the case of molding a mirror-like or matte-like molded product by the injection molding method, preferably, the thickness of the heat-insulating layer exceeds 0.1 111111, is less than 0.4 mm, and the thickness of the metal layer is the thickness of the heat-insulating layer. 13 or less, and 0.01 to 0.07 mm, more preferably, the thickness of the heat insulation layer is more than 0.12 mm and less than 0.3 mm, and the thickness of the metal layer is Is 1 to 5 or less and 1 to 100 or more in the thickness of the heat insulating layer, and is 0.02 to 0.06 mm.

When the grain-shaped molded article is formed by the injection molding method, preferably, the thickness of the heat insulating layer exceeds 0.1 111 ^ 1 and is less than 0.4 mm, and the thickness of the convex portion of the metal layer is preferably the thickness of the heat insulating layer. 13 or less and 0.01 to 0.07 mm, and the depth of the grain-shaped concave portion is 0.05 to 0.06 mm, and more preferably, the thickness of the heat insulating layer. Is more than 0.12 mm and less than 0.3 mm, the thickness of the convex part of the metal layer is 1 to 5 or less of the thickness of the heat insulating layer, and is 0.01 to 0.06 mm, and the grain shape is The depth of the concave portion is 0.005 to 0.04 mm. If the depth of the concave portion is too large, there will be a large difference in the mold surface reproducibility between the concave portion and the convex portion, or the draft of the molded product will be affected. On the other hand, if the depth of the concave portion is too small, the effect of forming the grain is reduced. '' In the case of forming mirror-like or eraser-like molded products by blow molding, it is preferable that the thickness of the heat insulating layer is 0.2 mm or more and less than 0.5 mm, and the thickness of the metal layer is 1 / 3 or less, and 0.002 to 0.1 mm, more preferably, the thickness of the heat insulating layer is 0.3 mm or more and less than 0.5 mm, and the thickness of the metal layer is 1 mm of the thickness of the heat insulating layer. Z 5 or less 1 Z 100 or more, and 0.04 to 0.06 mm.

In the case of forming a grain-shaped molded product by blow molding, preferably, the thickness of the heat insulating layer is 0.2 mm or more and less than 0.5 mm, and the thickness of the convex portion of the metal layer is 1% of the thickness of the heat insulating layer. 3 or less, and 0.01 to 0.1 mm, the depth of the grain-shaped recess is 0.05 to 0.09 mm, and more preferably, the thickness of the heat insulating layer is 0. 3 mm or more and less than 0.5 mm, the thickness of the convex portion of the metal layer is 1/5 or less of the thickness of the heat insulating layer, 1100 or more, and 0.01 to 0.08 mm. The depth of the grain-shaped concave portion is 0.005 to 0.07 mm.

In the present invention, when the surface of the metal layer has irregularities in the shape of a grain, the thickness of the metal layer at the thick portion of the metal layer (generally, the thickness of the projection of the metal layer) is covered with the heat insulating layer according to the molding method of the present invention. The reason why the thickness of the metal layer of the mold is set is to improve the reproducibility of the mold surface of the projections and reduce the conspicuousness of well lines and the like of the entire molded product.

The thickness of the metal layer is preferably uniform, and the thickness variation is preferably ± 20% or less, more preferably ± 10% or less. When the surface of the metal layer is uneven, the thickness of the metal layer in the convex portion or the thickness of the metal layer in the concave portion is preferably uniform, and the variation in the thickness is preferably ± It is 20% or less, and more preferably ± 10% or less. If the thickness of the metal layer has a large variation, the reproducibility of the mold surface at the portion where the thickness of the metal layer is large is deteriorated, and the portion having good reproducibility of the mold surface and the portion having the bad reproducibility tend to appear on the same molded product surface.

The present invention relates to a molding method for achieving both the mold surface reproducibility of the molded article and the molding cycle time. In order to keep the molding cycle time short, it is preferable to carry out molding with the main mold temperature set low. In the present invention, it is preferable to perform molding by setting the main mold temperature to 15 ° C. or higher and 100 or lower and a temperature obtained by subtracting 20 ° C. from the curing temperature of the synthetic resin. More preferably, the molding is performed at a temperature not higher than −30 ° C. from the softening temperature of the synthetic resin. The main mold temperature described here is the temperature at the time of molding of the main mold in the portion in contact with the heat insulating layer. If the main mold temperature is higher than this, the required cooling time in the mold will be longer, and therefore the molding cycle time will be longer and the molding efficiency will be lower. If the main mold temperature is set to a temperature higher than 100, the reproducibility of the mold surface is naturally improved, but it is not preferable from the viewpoint of molding efficiency. The main mold temperature is preferably 20 ° C or more and 90 ° C or less, and more preferably 25 ° C or more and 80 ° C or less. When the temperature of the main mold is lower than 15 ° C, dew condensation or the like easily occurs on the mold surface. The softening temperature described here is a softening temperature at which the deformation of the whole molded article is a problem. This is the softening temperature of the entire synthetic resin including (integral value described later (different from the softening temperature when calculating seconds · ° ο)).

In the present invention, molding conditions are selected such that the mold surface temperature drops below the aging temperature of the synthetic resin 5 seconds after the synthetic resin to be molded contacts the mold surface. That is, if the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin for 5 seconds after the synthetic resin comes into contact with the mold surface, the mold surface reproducibility is sufficiently improved, and after that, the mold surface temperature should be lower. Preferable in terms of molding cycle time. Further, in the injection molding method of the present invention, preferably, the condition is such that the mold surface temperature is lowered to (the synthetic resin's aging temperature minus 10 ° C.) 5 seconds after the synthetic resin comes into contact with the mold surface. It is molded and, more preferably, the surface temperature of the mold is lowered to (the softening temperature of the synthetic resin is lower than 20 ° C). This can be satisfied by appropriately selecting the thickness of the heat insulating layer and the metal layer, the resin temperature, and the mold temperature. The mold surface reproducibility of the molded product in injection molding is a problem within 5 seconds after the synthetic resin comes into contact with the mold surface, within 3 seconds for standard injection molding, and 2 for most standard injection molding. This is a problem within seconds. During that time, if the surface temperature of the mold is high and is equal to or higher than the curing temperature of the synthetic resin, it is preferable that the mold surface be rapidly cooled thereafter from the viewpoint of the molding cycle time. Accordingly, in the present invention, it is particularly preferable that the mold surface temperature falls to a temperature lower than the softening temperature of the synthetic resin two seconds after the synthetic resin comes into contact with the mold surface. If the mold surface temperature is higher than the plasticization temperature of the synthetic resin for nearly 20 seconds after the synthetic resin comes into contact with the mold surface, the mold surface reproducibility will naturally improve, but the molding cycle time will increase. , Can not be used economically.

When the surface of the main mold made of metal is covered with a heat insulating layer and the injected heated resin comes into contact with the surface, the surface of the mold is heated by the heat of the resin. The lower the thermal conductivity of the heat insulating layer, and the thicker the heat insulating layer, the higher the mold surface temperature.

The present invention relates to a heat-insulating layer coating metal in which a heat-insulating layer made of a heat-resistant polymer is present on a mold wall constituting a mold cavity of a metal main mold, and a metal layer adhered to the heat-insulating layer is present thereon. After the heated synthetic resin to be molded is in contact with the mold surface using the mold, the integral value of the (mold surface temperature-softening temperature of the synthetic resin) value (Δ Η) for at least 2 seconds and / or while the mold surface temperature is (synthetic resin softening temperature-10 ° C) or more (the mold surface temperature-(softening temperature of synthetic resin-10 ° C)) } A molding method for synthetic resin that is molded under molding conditions where the integrated value (Δΐι) of the value is 10 seconds or more. is there. The mold surface temperature is the interface temperature at which the heated synthetic resin to be molded contacts, and the mold surface temperature and the resin surface temperature are almost equal. In the present invention, the mold surface temperature and the resin surface temperature are used as having the same meaning. When the plasticized resin that has been heated and plasticized comes into contact with the cooled mold, the heat is taken away by the metal layer having a large heat capacity, and the mold surface temperature temporarily decreases, but immediately rises to the softening temperature of the synthetic resin. And then fall again. The mold surface reproducibility during molding was found to be largely dependent on two factors: the time during which the mold surface was above the softening temperature of the synthetic resin, and the number of times the temperature rose from the aging temperature to a higher temperature. Reached. That is, in the present invention, after the heated synthetic resin to be molded comes into contact with the surface of the mold, the integral value (Δ Η) while the surface temperature of the mold is equal to or higher than the curing temperature of the synthetic resin is 2 seconds · ° C or more, and Alternatively, when molding is performed under molding conditions with an integral value (Δίι) of 10 seconds · ° C or more, the mold surface reproducibility is improved. This integrated value is the area enclosed by the curve and the softening temperature line of the synthetic resin in the drawing of the time-dependent change curve of the mold surface temperature, or the curve and the (softening temperature of synthetic resin minus 10 ° C) line. Corresponds to the area surrounded by.

In injection molding, a preferable integral value (ΔΔ) is 2 seconds · ° C or more, 50 seconds or less, more preferably 5 seconds · ° C or more, 40 seconds · or less, particularly preferably. Is 7 seconds. And is 40 seconds · ° C or less, most preferably 8 seconds · ° C or more, 40 seconds · ° C or less. The preferred integral value (Δΐι) is 10 seconds or more and 100 seconds or less, and more preferably 12 seconds or more and 70 seconds or less. It is particularly preferably 15 seconds to ° C or more and 70 seconds or less, and most preferably 20 seconds to ° C or more and 70 seconds or less. In the blow molding, the required integral value becomes large because the force of pressing the synthetic resin against the mold surface is low and the time until pressure is applied after contacting the mold surface is long as compared with the injection molding. The preferred integral value (ΔΗ) in blow molding is 10 seconds · ° C or more, more preferably 20 seconds · ° C or more, and the preferred integral value (mmh) is 20 seconds · ° C. More preferably, 30 seconds or more.

When the surface of the metal layer is in the shape of a grain having irregularities, the integral value of the portion where the thickness of the metal layer is large (generally, the convex portion is thick) is used.

From the viewpoint of the molding cycle time, etc., the upper limit of the integral value is preferably 50 seconds · ° C or less, more preferably 40 seconds / ° C or less in the injection molding, and On the other hand, the integration value (A h) is preferably 1 0 0 ^s-e C or less, further preferred properly 7 0 seconds - ° c or less.

In blow molding, the integral value (ΔΗ) is preferably 200 seconds or less, and more preferably 100 seconds · ° C or less, and the integral value (Δh) is 400 seconds. · ° C or less is preferred, and more preferably 300 seconds · ° C or less. In the present invention, from the viewpoint of the molding cycle time, it is preferable to select molding conditions and a mold structure in which the integral value is small within a range where the mold surface reproducibility is practically achieved.

The aging temperature of the synthetic resin used in calculating the integral value (ΔΗ) and the integral value (A h) is a temperature at which the synthetic resin can be easily deformed. In the case where the compound compounded in the synthetic resin is an organic material which is easily deformed during molding of rubber or the like or a compound dissolved in the synthetic resin, it is the softening temperature of the entire synthetic resin including the compound. On the other hand, for synthetic resins containing fillers that do not deform in the synthetic resin when molding fibers such as glass fibers, whiskers, carbon fibers, and inorganic powders such as calcium carbonate, the base material excluding these inorganic fillers is used. It is the aging temperature of the synthetic resin. In order to improve the mold surface reproducibility by molding a synthetic resin containing a filler that does not deform in the synthetic resin during molding, it is preferable that the surface of the molded product be covered with the base synthetic resin. It is preferable that the inorganic filler is hardly exposed on the surface of the molded product. Therefore, when the resin comes into contact with the mold surface during molding, it is necessary for the base synthetic resin to pass through the gap between the inorganic fillers near the molded product surface and reach the mold surface, and the fluidity of the base resin Are directly related to mold surface reproducibility. Therefore, the softening temperature for calculating the integral value of a synthetic resin containing a filler that does not deform in the synthetic resin during molding is indicated by the softening temperature of the base resin. The softening temperature is concerned with the deformation of the whole molded article, and is the softening temperature of the whole resin including the compound.) The curing temperature is the vicat softening temperature for non-crystalline resin (ASTMD 155) The thermal deformation temperature for hard crystalline resin (ASTMD 648 load 18.6 kcm ² ) and the thermal deformation temperature for crystalline resin Temperature (ASTMD 648 load 4.6 kg Z cm ² ). The non-crystalline resin is, for example, polystyrene, rubber-reinforced polystyrene, polycarbonate, or the like. The hard crystalline resin is, for example, polyoxymethylene, nylon 6, nylon 66, or the like. Is, for example, various polyethylenes, polypropylenes and the like. Further, in the present invention, it is preferred that the maximum temperature at which the temperature rises immediately after the temperature of the mold surface to be heated once drops is equal to or higher than (curing temperature of synthetic resin + 20 ° C.).

In the present invention, the heat-insulating layer and the metal are formed so that the integral value (ΔΗ) can be molded under molding conditions of 2 seconds' ° C or more and / or the integral value (Ah) is 10 seconds · ° C or more. Select layer thickness, type of synthetic resin, molding conditions such as resin temperature and mold temperature.

An object of the present invention is to improve mold surface reproducibility while maintaining a short molding cycle time. For this purpose, if the change in the mold surface temperature necessary for improving the mold surface reproducibility can be obtained, the integral value (ΔΗ) and the integral value (Δΐ) necessary for improving the mold surface reproducibility can be obtained. If possible, a rapid decrease in the mold surface temperature is necessary to shorten the molding cycle time. Furthermore, the integral value (ΔΗ) and the integral value (Ah) need to be higher than the value required to obtain the mold surface reproducibility, but it is not necessary to make it much larger than that, A value close to is preferred.

In order to achieve this, in the present invention, after 5 seconds from the contact of the synthetic resin to be molded with the mold surface, the mold surface temperature is preferably equal to or lower than the softening temperature of the synthetic resin. The molding is carried out under the molding conditions of not more than (0 ° C) or more preferably (the curing temperature of the synthetic resin is not more than 20 ° C). This is a limitation that does not increase the molding cycle time. More preferably, the temperature of the main mold is set at 100 ° C or lower at 15 ° C or higher, and at a temperature not higher than the softening temperature of the synthetic resin minus 20 ° C, preferably at 20 ° C or higher. At 90 ° C or lower, and at a temperature not higher than the softening temperature of the synthetic resin minus 20 ° C, and particularly preferably at a temperature of 25 ° C or higher and 80 ° C or lower, and 3 ° C from the softening temperature of the synthetic resin. Set the temperature below 0 ° C or less, set the thickness of the heat insulation layer to more than 0.1 mm and less than 0.5 mm, and then specify the range of the integral value (ΔΗ) and the integral value (Ah). ing.

Changes in mold surface temperature during injection molding or blow molding can be calculated from the temperature, specific heat, thermal conductivity, density, etc. of the synthetic resin, main mold, and heat insulating layer. For example, ABAQUS (U.S.A., software of Harbbit. Karlson & Sorensen, Inc.), ADINA and ADI NAT (software developed at Massachusetts Institute of Technology), etc. It can be calculated by transient heat conduction analysis using the element method. The integrated value (ΔΗ) and the integrated value (Ah) of the present invention are indicated by values calculated from the calculated value of the change in the mold surface temperature. This calculation is based on the shearing of the plastic during injection molding. The heat generation and the heat transfer coefficient of the film between the layers are ignored. The mold surface temperature change shown in the drawings and the like of the present invention is a value calculated using ABAQUS under the above conditions.

Although the metal layer of the present invention can be coated by various methods, it is well coated by plating. The plating described here is a chemical plating (electroless plating) and an electrolytic plating. In the present invention, it is preferable that the plating be performed through some of the following steps. That is, first, the surface of the heat insulating layer is made fine and uneven, and then the chemical plating is performed.

Pretreatment—Chemical corrosion (Chemical etching with strong acid solution of strong oxidizing agent: Makes the surface moderately fine irregularities) —Neutralization ”* Sensitivity treatment (Adsorption of metal salts with reducing power on synthetic resin surface) Activation effect is shown.)-Activation treatment (noble metal such as palladium having catalytic action is applied to the resin surface) → Chemical plating (chemical nickel plating, chemical copper plating, etc.)-Electrolytic plating (electrolytic nickel plating) , Electrolytic copper plating, electrolytic chrome plating, etc.).

Calcium carbonate, silicon oxide, titanium oxide, barium carbonate, barium sulfate, and alumina are used as heat insulating materials that form at least the outermost surface of the heat insulating layer in order to increase the adhesion between the heat insulating layer and the metal layer. A fine powdery etching aid such as a fine powder of an inorganic substance such as an inorganic substance or an organic substance such as various polymers, etc., is blended, and the powder is eluted by chemical corrosion to form a surface having an appropriate fine unevenness, and then subjected to plating. Can be used very well. It is preferable that about 1 to 30% by weight of the fine powder etching aid is mixed with the heat insulating material.

Next, the chemical nickel plating that can be favorably used in the present invention will be described in detail. Chemical plating involves reducing and depositing metal ions on a metal with a reducing agent. Generally, chemical plating must satisfy the following conditions. (1) The reducing agent must be stable without self-decomposition while the plating solution is adjusted. (2) The product after the reduction reaction does not precipitate. (3) The deposition rate can be controlled by pH and liquid temperature. In chemical nickel plating, sodium hypophosphite, hydrogenated boric acid, and the like are used as a reducing agent, and sodium hypophosphite is particularly preferably used. In order to satisfy the above conditions, auxiliary components (PH adjusters, buffers, accelerators, stabilizers, etc.) are added to the chemical plating solution in addition to the main components (metal salts, reducing agents). When sodium hypophosphite is used as a reducing agent with various auxiliary components, the resulting nickel plating contains phosphorus. In the present invention, the preferred chemical nickel layer which adheres to the heat insulating layer contains 1% by weight or more and less than 5% by weight of phosphorus, more preferably 2% by weight or more and 5% by weight or less. The thickness of the chemical Nikkerume luck layer is generally sufficient with a thin layer of about called primers, are favored properly 0.. 1 to 5 m, further preferred properly is 0. 2 ~ 2 _tf m extent. In the heat-insulating-layer-coated mold used in the present invention, it is necessary that the chemical nickel plating layer be firmly adhered to the heat insulating layer. Therefore, in the initial stage of the chemical nickel plating, the temperature of the plating solution is lowered and the pH is lowered. It is extremely preferable to reduce the plating speed by adjusting the thickness, to generate plating particles having a small particle size, and to cause the plating to enter into the fine irregularities on the surface of the heat insulating layer. After the plating layer with a certain thickness is formed, the plating speed is increased to perform plating efficiently. As a result, the nickel plating layer in contact with the heat insulating layer becomes a chemical nickel plating layer containing 1% by weight or more and less than 5% by weight of phosphorus, and the nickel plating layer on the nickel plating layer is an electrolytic nickel plating layer. It becomes an electrolytic chrome plating layer, a chemical nickel plating layer containing 5 to 14% by weight of phosphorus, and an electrolytic copper plating layer. Chemical nickel plating with a high phosphorus content directly on the surface of the heat insulating layer, especially chemical nickel plating containing more than 8% by weight of phosphorus, generally increases the size of the nickel-produced particles and reduces the adhesion of the plating layer. .

A detailed description will be given of the metal plating on the polyimide layer surface most suitable as the heat insulating layer in the present invention. Metal plating on the polyimide surface begins with a polyimide surface treatment. As described in U.S. Pat. Nos. 4,775,449 and 4,842,946, the polyimide surface is treated with an alloy or the like. It is common to do. In other words, polyimide is weak to alkali and its surface is activated. However, the metal layer on the surface of the heat insulating layer is subjected to severe cooling and heating cycles during molding of the synthetic resin, so it is necessary to have sufficient adhesion strength to withstand the severe cooling and heating cycles. As a result of various studies, we demonstrated polyimide containing a fine powdered etching aid such as calcium carbonate, titanium oxide, or alumina on the polyimide surface layer, and etched the surface with a strong acid solution of a strong oxidizing agent. Then, fine powder of calcium carbonate, titanium oxide, alumina, etc. present on the surface layer and a part of polyimide are eluted to make the polyimide layer surface with moderate fine irregularities, then neutralization and sensitivity It has been discovered that a method of performing chemical nickel plating through the activating treatment and the activation treatment can be favorably used in the present invention. Was. As the fine powder, an organic substance such as a fine powder of a crosslinked rubber or a fine powder of a poorly soluble polymer can be used.

Specific examples of the plating that can be favorably used in the present invention are shown below in more detail. Fine powder of fine calcium carbonate, titanium oxide, alumina, etc., having an average particle size of about 0.01 to 5 m, 1 to 30% by weight based on polyimide, preferably 5 to 25 % By weight, and fully kneaded with the polyimide and blended as the outermost surface layer. In this case, the entire polyimide layer may be a compound polyimide, or only the outermost surface layer may be a compound polyimide. These fine powders are easily agglomerated, and are sufficiently kneaded with a polyimide precursor solution to be sufficiently dispersed, applied to a mold surface, and heated to form a polyimide. Next, the polyimide surface is subjected to an etching treatment with a strong acid solution containing chromic acid, sulfuric acid, phosphoric acid, etc. to elute a part of the fine powder and polyimide on the surface layer, and to form an appropriate surface on the polyimide surface. Fine irregularities are formed, and then, after neutralization, sensitization, and activation, chemical nickel plating is performed using sodium hypophosphite or the like as a reducing agent. Chemical nickel plating is performed at a low temperature and at a low speed in a weakly alkaline state to reduce the size of generated nickel particles and to allow nickel to enter even into the fine irregularities on the polyimide layer surface. A method of remarkably improving the adhesive force by incorporating the nickel metal plating is a very preferable method for the present invention.

In general, chemical nickel plating is in acidic condition, and the temperature is raised to improve plating efficiency. When sodium nickel hypophosphite is used as a reducing agent and chemical nickel plating is carried out at low temperature and low speed in a weak alkaline state, the phosphorus content in nickel nickel falls to 1% by weight or more and less than 5% by weight. Become. A preferred composition of the chemical nickel layer in contact with the heat insulating layer of the present invention contains 1% by weight or more and less than 5% by weight of phosphorus.

Performing the chemical nickel plating at a low temperature and at a low speed as described in the present invention means that the chemical nickel plating is performed at a lower temperature and at a lower speed than the commonly used chemical nickel plating, but preferably 50 ° C or less and 5 ° C or less. More preferably, the temperature is 40 ° C or less and 10 ° C or more, and the speed is preferably 10 m or less and 0.1 m or more per hour.

Various types of metal layers can be placed on the thin chemical nickel plating that firmly adheres to the heat insulation layer. Preferred specific examples of the plating further attached on the thin chemical nickel plating are shown below. (1) Chemical nickel plating (containing 5 to 18% by weight of phosphorus)

(2) Electrolytic chrome plating (hard chrome plating, etc.)

(3) Electrolytic nickel-plate (such as glossy nickel-plate, semi-gloss nickel-plate, non-light nickel-plate)

(4) Chemical copper plating

(5) Electrolytic copper plating

It is preferable that at least one layer or two or more layers selected from these methods are coated. For example, if electrolytic copper plating and Z plating or chemical copper plating are performed on a thin-layer chemical nickel plating, and nickel plating is further performed thereon, the adhesion of the plating is improved and it can be used favorably.

It is preferable that the outermost surface of the metal layer has a hard nickel layer that is hard to be scratched, such as a nickel metal layer or a hard chrome metal layer, of 0.5 m or more, more preferably 1 to 50 m, and particularly preferably 2 m or more. Preferably it is ~ 30 m.

When the synthetic resin to be molded contains 5 to 65% by weight of inorganic pitting material such as glass fiber, whiskers and calcium carbonate, more preferably more than 20% by weight and 65% by weight or more In particular, when 30 to 50% by weight of an inorganic filler is blended, the hardness of the metal layer on the outermost surface of the mold surface is determined by the inorganic filler in the synthetic resin. It is preferable that the hardness is equal to or higher than the hardness of the material. This hardness is relative and means that the metal layer is not easily scratched when the two are rubbed together. When comparing glass fiber and hard chrome plating, it can be compared by rubbing the hard chrome plating with glass fiber. It is difficult to directly compare the hardness of an object with a numerical value when the type of material is different, but in the present invention, the hardness is compared with Vickers hardness (HV). Vickers hardness (HV) is a method of using a diamond pyramid with an apex angle of 13 6 degrees as an indenter and expressing the hardness by dividing it by the surface area of the indented dent that caused the load. It is shown in kg / mm ^2. The following table shows the typical plating and Vickers hardness (HV) of glass. Table 3

The hardness of the chemical nickel plating (electroless nickel plating) depends on the phosphorus content, but also depends on the heat treatment after plating. The change in hardness due to the heat treatment of nickel plating is described in ISODIS4527.

E-glass is often used as glass fiber in synthetic resins. E-glass is a glass developed for electrical products and is close to alkali-free glass. Its composition is S i 0 ₂ 5 2 to 56 wt%, Al ₂ 0 ₃ 1 2 to 16 wt%, CaO 16 to 25 wt%, MgO 0 to 6 wt%, B ₂ O ₃ 8 to 13 wt% , N a ₂₀ and K or K _{200 to} 3 wt%. When molding a synthetic resin containing a large amount of this glass, the hardness of the metal layer on the outermost surface of the mold is preferably equal to or greater than the hardness of this glass. When the hardness of the metal layer described in the present invention is equal to or higher than the hardness of the inorganic filler in the synthetic resin, the Vickers hardness of the metal layer is determined by the Vickers hardness of the inorganic filler in the synthetic resin. Hardness is greater than 100), preferably the picker hardness of the metal layer is greater than the Vickers hardness of the inorganic filler, and more preferably the Vickers hardness of the metal layer is less than that of the inorganic filler. (Vickers hardness + 50).

These metal features that can be favorably used in the present invention are in intimate contact with the heat insulating layer at the interface of fine irregularities. Therefore, the interface between the plating layer and the heat insulating layer has a shape in which the plating layer and the heat insulating layer enter each other. In this case, the thickness of the metal layer described in the present invention is the thickness of the portion where the metal occupies 50% by volume or more, and the thickness of the heat insulating layer is the thickness of the portion where the heat insulating material exceeds 50% by volume.

The surface of the metal layer of the present invention can be mirror-like, matte-like, rugged, lens-like, or the like.

Various methods can be used to make the surface of the metal layer formed by plating into a grain shape. The etching method can be used favorably. The etching method is best used. If the outermost layer of the mold is a metal that can be etched with an acid solution such as electrolytic nickel plating, electrolytic copper plating, chemical plating, etc., etching used for graining of general metal molds Graining can be performed in the same manner as the method. That is, a method in which the surface of the metal layer is masked in a grain shape using an ultraviolet curable resin and then grained by acid etching can be favorably used. When the metal layer is nickel plating, chemical nickel plating having a phosphorus content of 8% by weight or more is difficult to be etched by an acid, and chemical nickel plating having a lower phosphorus content is easily etched.

The phosphorus content and acid resistance of Chemical Nickel Macchi are shown in Plating and Surface Face Finishing, 79, No. 3, P. 29-33 (1992), etc. The higher the phosphorus content, the better the acid resistance. In Table 1 of the above-mentioned literature, the acid resistance is as follows: G 0 od at phosphorus content of 10 to 12% by weight, air at 1 to 4% by weight at 7 to 9% by weight. oor. The phase diagram of the Nigger-Phosphorus alloy shows that the phosphorus content is 0-4.5% by weight in S phase, 11-15% by weight is in A phase, and 4.5-11% by weight is in γ phase. It is a three-phase mixture. The seven phases are excellent in corrosion resistance to acid, and the corrosion resistance is large when the phosphorus content is 8% by weight or more, which is generally called high phosphorus content. Even in electrolytic nickel plating, the etching properties vary depending on the composition, and nickel plating having a large phosphorus content is difficult to be etched with an acid. The depth of the grain by etching can be adjusted by adjusting the etching time, a combination of a metal layer which is easily etched and a metal layer which is hardly etched. Further, on the outermost surface of the metal layer after the grain formation, a thin metal layer having excellent corrosion resistance and / or a metal layer having a high hardness, that is, a chemical nickel plating layer having a high phosphorous content ゃ an electrolytic hard chrome plating. A layer can be used well.

There are various methods for forming the mold surface into a Fresnel lens or lenticular lens shape, but the following methods can be used favorably.

(a) A method in which a metal layer formed by plating is cut into a lens shape by a machine tool and Z or polished. (b) A heat insulating layer is cut into a lens shape by a machine tool, and the lens surface is plated. Then, the surface is cut and / or polished again with a machine tool. (C) Using a preformed lens model, the surface is coated with a metal layer by electroforming, and the metal layer is separated. Then, a thin metal layer on the lens surface can be created and then attached to the heat-insulating layer. In the molds made by the methods (a) and (c), the thickness of the heat insulating layer is almost constant, and the thickness of the metal layer fluctuates like a lens. On the other hand, in the mold made by the method (b), the thickness of the heat insulating layer fluctuates like a lens, and the thickness of the metal layer becomes almost constant. The present invention includes both molds. If the thickness of the heat insulating layer fluctuates, the thickness of the heat insulating layer in the thin portion is used as the heat insulating layer thickness.

In the lens formed by the heat-insulating layer-coated mold described in the present invention, the acute angle portion of the mold cavity is sufficiently reproduced, and a good lens is obtained. In other words, when a lens having an acute angle portion of the mold cavity is molded by a conventional mold, the synthetic resin cannot sufficiently enter the acute angle portion of the mold cavity, and a good lens that sufficiently reproduces the angle portion is formed. In order to mold, it was necessary to set the mold temperature extremely high. Increasing the mold temperature has the disadvantage of increasing the molding cycle time and reducing productivity. According to the present invention, an increase in the molding cycle time is kept very small, and a good lens having a good reproduction of the corner can be obtained.

A similar problem arises when obtaining a diffusive molded product with a high diffusivity with a fine uneven surface, and a molded product in which the fine irregularities on the mold surface are sufficiently reproduced Molding was difficult with a mold. With the mold of the present invention, it is possible to obtain a highly diffusive molded product in which the unevenness of the mold surface is sufficiently reproduced, and in particular, to mold a transparent synthetic resin by injection molding to form a highly transparent, highly diffused plate, etc. This is an extremely preferred molding method. In recent years, a backlight for a liquid crystal display device has been required to have a high transmission and a high diffusion plate with excellent performance. In other words, there is a demand for a high transmission and high diffusion plate having a high total light transmittance and a low parallel light transmittance. Conventionally, these high transmission and high diffusion plates disperse incident light by dispersing fine powder having a different refractive index from the transparent synthetic resin such as calcium carbonate and barium sulfate in a transparent resin such as methacrylic resin. Plates have been used. However, it was difficult for these fine powders to absorb incident light and obtain a sufficiently high transmission and high diffusion plate. In the present invention, the mold according to the present invention is used by using the mold of the present invention in which the surface of the mold has a very small number of surfaces parallel to the surface of the mold, that is, the surface of the fine irregularities in which the concaves and convexes of the fine irregularities are formed. As a molded product in which the fine uneven surface of the mold surface is sufficiently reproduced by the method, a molded product capable of sufficiently diffusing incident light on the molded product surface can be obtained. As a result, it was found that a high transmittance and high diffusion plate with a sufficiently small parallel light transmittance could be obtained without using a small amount of fine powder mixed with the synthetic resin or without compounding. The relationship between the total light transmittance T (%), the diffuse light transmittance D (%), and the parallel light transmittance P (%) measured by ASTM-D1003 is as follows.

T = D + P

P <0 .0 4 5 T

This is one of the preferred uses of the molding method of the present invention.

Next, another example of a preferable use of the molding method of the present invention will be described.成形 Molded products with a matte appearance such as home appliances and office equipment with an eld part, that is, molded products that are required to have effects completely opposite to those of the high-permeability, high-diffusion plate with the high diffusion rate described above. The present invention can be favorably used for molding. A mold for molding such a molded article is a matte which is obtained by forming the metal layer surface or a part of the metal layer surface of the heat-insulating layer-coated mold described in the present invention by a multi-stage sand-plast treatment and / or a multi-stage etching treatment. The use of a mold having a convex surface can be favorably used. More preferably, the mold surface metal layer has a lower hardness and / or a higher etchability compared to its inner metal layer, and A mold having a metal layer having a layer is a mold having an candy-like surface formed by a multi-stage sand-plast treatment and / or a multi-stage etching treatment. In particular, it is more preferable that the etching speed of the metal layer of the metal surface of the metal mold is at least twice the etching speed of the inner metal layer, and the above-mentioned metal layer is made into a 16 erased surface by multi-stage etching. Can be favorably used. It is preferable to use a mold having this matte surface, and the manufacturing method thereof will be described in further detail below.

Conventionally, the method of making the mold surface forming the mold cavity of a general mold a matte surface is a method of roughening the mold surface by a sand blast method. In the case of a mold coated with a heat-insulating layer, the sandblasting method can be considered first to roughen the surface of the heat-insulating layer so that the surface becomes dull. When the surface of the heat-insulating layer of the heat-insulating layer-coated mold or the metal layer on the surface of the heat-insulating layer was subjected to sand-blasting to form an exposed state, and injection-molded with rubber-reinforced polystyrene or the like, the mold surface was uniform It was found that the molded synthetic resin injection-molded product did not have a uniform matte shape, and was extremely easily scratched by human nails or the like, despite the fact that it had a fungus-colored form. In other words, unsightly well line dents are eliminated, but the injection molded product is easily damaged, and the general part and the weld part of the molded product and the Z or general part and the resin flowing end are uneven. It is a molded product that shows a remarkable defect phenomenon that it easily becomes a shiny matte surface. The present invention provides a method for solving the problems inherent in molded articles formed by using these molds coated with a heat-insulating layer having an erased surface II. That is, economical molding of a synthetic resin molded product with excellent appearance that achieves a reduction in well-lined appearance, uniform matte surface, improved scratch resistance, etc. without significantly lengthening the molding cycle time. A molding method is provided.

In particular, the metal layer on the heat insulating layer surface preferably has two or more metal layers such that the surface metal layer on the mold cavity side has lower hardness and / or greater etching properties than the inner metal layer. I like it. When the number of the metal layers is two or more, the thickness of the surface metal layer on the mold cavity side is preferably 1 Z2 or more of the thickness of the entire metal layer. In order to make the metal layer in a matte state by multi-stage sand blasting, it is preferable that the picker hardness value of the surface metal layer is smaller than the (Vickers hardness-150) value of the inner metal layer. In other words, the metal that is easily made uneven by the sand blasting process forms the surface metal layer. It is preferred that The hardness of an object is hard to compare directly with a numerical value when the type of material is different, but in the present invention, the hardness is compared by Vickers hardness (HV). Vickers hardness (HV) is a method that uses a diamond pyramid with an apex angle of 13.6 degrees as an indenter and expresses the hardness by dividing it by the surface area of the thick indent that caused the load. The unit is kg. / shown in mm ^2. The sand blasting treatment described here is a sand blasting treatment that makes the surface of a general mold saturate and yields, and the inorganic particles of various particle sizes and various shapes such as carbon random, glass, etc. are mixed with a pressurized gas. It is to spray the mold surface together to make the mold surface matte.Multi-stage sand blasting is the process of sand blasting particles having different particle sizes, shapes, materials, etc. twice or more. is there. It is preferable to use a combination of sandblasts of angular particles and those of spherical particles. The multi-stage sand blasting process of the present invention is to perform different sand blasting processes at least twice, preferably 3 to 6 times. In this case, it is not necessary that all of the third to sixth sandblasting processes be different. For example, two types of processing, A processing and B processing, may be repeatedly performed. It is difficult to obtain the erasing surface required by the present invention by one-step sand-plast treatment. The hardness of chemical nickel plating (electroless nickel plating) depends on the phosphorus content, but also depends on the heat treatment after plating. The change in hardness due to the heat treatment of nickel plating is described in ISODIS 457, etc.

The multi-stage etching described in the present invention means that the etching process is repeatedly performed in two or more stages, preferably in three to ten stages, and more preferably in four to eight stages. With a single-step etching process, it is difficult to obtain the matte surface required by the present invention. When the surface of the metal layer is made to be in a matte state by multi-stage etching, it is preferable that the etching rate of the metal layer on the mold surface is at least twice the etching rate of the metal layer on the inner side, and more preferably 3 times. More than twice, particularly preferably more than 5 times.

If the metal layer is a metal that can be etched with a general etching solution such as electrolytic nickel plating, electrolytic copper plating, chemical nickel plating, etc., the same etching method used for graining of general metal molds is used. Can be used. That is, the surface of the metal layer is partially masked with an ultraviolet curable resin, and then etched with a ferric chloride solution or an acid solution. By repeating this masking and etching, The face metal layer is made to be in an erased state.

When the metal layer is nickel plating, chemical nickel plating having a phosphorus content of 8% by weight or more is difficult to etch, and chemical nickel plating having a lower phosphorus content is easily etched. The inner metal layer of the metal layer of the present invention is preferably a high phosphorus content nickel having excellent corrosion resistance, and the surface metal layer is preferably nickel having a phosphorus content of less than 8% by weight and 3% by weight or more. Even in electrolytic nickel plating, the etching properties vary depending on the composition, and vary depending on the sulfur content and the phosphorus content. Higher phosphorus content results in better corrosion resistance.

Performing the multi-stage sand-plast process and / or multi-stage etching process described in the present invention includes performing a total of two or more processes using the sand-plast process and the etching process together. Even in this case, it is preferable to perform the processing three times or more in total. The method that combines multi-stage etching and single-stage or multi-stage sand blasting is the best method.

The severely erased surface of a synthetic resin injection molded product such as rubber-reinforced polystyrene molded by this mold is preferably a scratch of 2 B or less in a pencil scratch test, and is preferably marked with a hardness of B or less. Has good fine uneven surface with no scratch resistance. More preferably, it has abrasion resistance to human nails. The pencil pull test is measured according to JIS K5401. Conspicuous wounds are those that are easily visible to the naked eye.

When molding is performed using a mold coated with a heat insulating layer, it is possible to apply the pressure necessary for reproducing the mold surface to the synthetic resin on the mold wall surface in a state where a solidified layer has not yet been formed on the mold surface. If the mold surface of the heat-insulating layer-coated mold is in a matte shape with fine irregularities, the synthetic resin will flow sufficiently into the concaves of the fine irregularities on the mold surface before the solidified layer is formed, and the mold surface will be sufficient. Will be reproduced. Even if the concave portion of the fine irregularities on the mold surface is sharp, it will be sufficiently reproduced. As a result, the matte-shaped molded article formed by the heat-insulating-layer mold has sharp projections of the fine irregularities on the surface thereof, and the sharp corners of the surface irregularities are damaged when human nails or the like come into contact with the molded article. It is easy to be scratched. In the heat-insulating layer-covered mold which has been subjected to the multi-stage etching and / or multi-stage sand-plasting of the present invention, the concave portions of the fine irregularities in the outermost metal layer of the mold are made obtuse, and the synthetic resin is sufficiently deep into the concave portions of the fine irregularities. It is intended to obtain a molded product with an uneven surface that is hardly scratched even if it enters the surface. In other words, multi-stage etching is necessary to make a mold with the bottom of the concave part of the fine unevenness on the metal layer surface formed at an obtuse angle. It is preferable to use a mat and a multi-stage sandplast to make the matted shape, and it has been found that it is extremely preferable to combine this method of forming the matted surface with the mold for coating the heat insulating layer of the present invention. Invented the invention.

In the present invention, an injection molding method or a blow molding method can be favorably used.

In injection molding, the mold surface reproducibility differs depending on the temperature of the synthetic resin to be injected, the temperature of the main mold, the injection pressure, the flow velocity of the synthetic resin in the mold, and the like. The method of the present invention is more effective when the average flow velocity in the mold of the synthetic resin is 20 to 300 mm / sec, and can be used favorably. More preferably, it is formed well by low-speed injection of 30 to 200 mmZ seconds. The lower the flow velocity in the mold, the lower the mold surface reproducibility generally becomes worse. The present invention is more effective at low-speed injection molding in which mold surface reproducibility is generally poor, and can be used particularly well. Injection compression molding and gas assist injection molding are generally low-speed injection molding. The average speed in the mold can be generally calculated by dividing the resin flow distance from the gate of the mold cavity to the flow end by the flow time of the synthetic resin in the mold. This value is also used in the present invention. The present invention has a large effect in the case of low-speed injection, but is not limited to low-speed injection molding, and can be used in general high-pressure injection molding.

In blow molding, the mold temperature depends on the temperature of the synthetic resin to be blown, the temperature of the main mold, the blow pressure, and the time from when the parison to be blown comes into contact with the mold surface until the blow pressure is sufficiently applied to the inner surface of the molded product. Surface reproducibility is different. In the present invention, the time from when the parison to be blown comes into contact with the mold surface to when the blow pressure is sufficiently applied to the inner surface of the molded article is preferably 1 to 10 seconds, more preferably 2 to 10 seconds. Formed in 8 seconds, particularly preferably 2-5 seconds. In particular, in the present invention, after the synthetic resin comes into contact with the mold surface, if a blow pressure is applied while the mold surface temperature is maintained at or above the softening temperature of the synthetic resin, the mold surface reproducibility is sufficiently improved, and within 5 seconds. It is particularly preferred that blow pressure be applied to the air.

The present invention will be described with reference to the drawings.

FIGS. 1 to 27 show the results obtained by calculating changes in the mold surface temperature and the like. As described above, the change in the mold surface temperature can be calculated by transient heat conduction analysis using software such as ABAQUS. Next, the calculation method will be described in more detail. Since the thickness of the Nigel layer and polyimide layer is considerably smaller than the thickness of the resin product, the phenomenon can be described by one-dimensional heat transfer. Think of it as a lead problem. In the steady state, the governing equation is given by

k (d ² T / dx ² ) = 0

Where k is the thermal conductivity of the material, T is the temperature, and X is the position.

The heat flux is given by the following equation from Fourier's law.

q =-k (d T / d x)

Where Q is the heat flux. Using the finite element method from these equations, the simultaneous equations are displayed in a matrix as shown below.

[κ] m = {?}

Where [K] is the heat transfer matrix, {T} is the overall nodal temperature vector, and {F} is the heat flux vector. If the heat transfer matrix [K] and the heat flux vector {F} are known, the simultaneous equations can be solved, and the nodal temperatures can be obtained.

The actual calculation can be performed using commercially available general-purpose structural analysis software. Here, the calculation was performed using ABAQUS. In this calculation, the heat transfer at the boundary between the synthetic resin and the metal layer and the heat conduction in the main mold are ignored because the effects are extremely small.

The values of the thermal conductivity and the specific heat used in the CAE calculation of the change in the mold surface temperature during molding according to the present invention use the actually measured values and the values from various documents. That is, for polyimide, an actually measured value of polyimide used as a heat insulating layer in the embodiment is used. For polystyrene, the thermal conductivity is H. Loboand R. Newman: Use the value reported in SPEANTEC '90, 862, and the specific heat is J. Brandrup, E.H.I. mm ergut edition Use the values described in rPoolymerH andbookJ John Wiley & Sons. For polyoxymethylene, the values described in “Human's Hashimoto's Thermal Diffusivity of Polymers, Specific Heat Capacity, Thermal Conductivity Data Handbook 1994” published by Unites Co., Ltd. are used. Strictly speaking, the thermal conductivity and the like differ depending on measurement conditions such as temperature and pressure at the time of measurement. In the present invention, the influence of temperature is considered, but the influence of pressure is not considered. For the relationship between the thermal conductivity of the polymer and the pressure at the time of measurement, refer to the molding process, V o 8 (2), 92 (1 996), SPE, ANT EC '90, 86 2 (1 9 90), molding process '90, 1339 (1990), etc., but it differs depending on the measurement method and is not clear, so the thermal conductivity at atmospheric pressure is used. Shall be used. The density, polystyrene 8 8 4 k gZm ^3, Polio Kishimechiren is 1 4 2 0 kg / m ^3, Porii mi de is the 1 4 2 0 kg / m ³ using, respectively. Epoxy resins vary greatly in performance depending on the type of epoxy resin and its curing agent, and in general, are often used in combination with compounds such as inorganic substances. The typical values of thermal conductivity, specific heat, and density shall be used, and the values in the Mechanical Design Handbook (3rd edition, published in 1992 by Maruzen Co., Ltd.) shall be used as they are. That is, the thermal conductivity value of the epoxy resin is 0. 3 WZM · K, the specific heat value 1.1 «1 Bruno 2 *! <, Density is used regardless of the 1 8 5 0 2 111 ³ temperature and pressure. The values for ceramics, nickel and steel are quoted from the Chemical Society of Japan, Chemical Handbook, Basics (Maruzen Co., Ltd.). The thermal conductivity of the ceramics is 2.1 WZ (m · K), the specific heat is 454 JZ (kg · K), and the density is 5700 kg / m ³ .

Further, the CAE calculation of the change in the mold surface temperature of the present invention does not take into account the heat generated by resin shearing during molding. FIG. 30 is a diagram showing a temperature distribution of a resin cross section by calculating a CAE of a rise in resin temperature due to shear heat generation during injection molding of rubber-reinforced polystyrene. CAE calculation conditions are as follows: resin is Asahi Kasei polystyrene 492, resin temperature is 240 ° C, mold temperature is 50 ° C, mold is steel, mold cavity is 2 mm in thickness, side gauge The flow distance from the mold to the flow end is 290 mm, and the resin flow time of the mold cavity is 0.4 seconds (injection speed of 72.5 mm, seconds) and 1.0 second (injection speed of 290 mm) mmZ seconds). Figure 30 shows the temperature distribution of the resin cross section immediately after the resin filled the mold cavities at the positions 25 mm and 144 mm from the gate. In the case of high-speed injection with an injection speed of 725 mmZ seconds, the amount of heat generated by shearing is large and the temperature of the resin rises significantly, but the lower the injection speed, the lower the heat generation, and the injection speed is 290 mmZ seconds Then, the heat generation decreases. In the case of low-speed injection at an injection speed of 20 to 300 mmZ seconds, in which the present invention can be used particularly well, the factor of shear heat generation is small, and shear heat generation is not taken into account. FIGS. 28 and 29 show the temperature dependence of the thermal conductivity (λ) and specific heat (C ρ) of each resin used in the present invention. The CA Ε calculation described in the present invention uses the heat shown in these figures. Use values for conductivity and specific heat.

Figures 1, 2 and 3 show that the temperature of the steel main mold was 50 The figure shows the calculated value of the change in the temperature distribution near the mold surface when injection molding was performed at a temperature of styrene (indicated by HIPS in the figure) of 240.

The numerical value of each curve in the figure indicates the time (second) since the heated synthetic resin came into contact with the cooled mold surface. The heated synthetic resin comes into contact with the mold surface and is rapidly cooled (Fig. 1). When the main mold surface is covered with a heat insulating layer, the mold surface receives heat from the heated synthetic resin and rises in temperature. As shown in the figure, when the mold surface is covered with a heat insulating layer (polyimide) of 0.1 111 111 and 0.3 mm (Figures 2 and 3), it comes into contact with the synthetic resin (rubber reinforced polystyrene). The temperature rise on the surface of the heat insulating layer increases, and the rate of temperature decrease also decreases.

Figure 4 shows the mold when heated synthetic resin (rubber reinforced polystyrene) comes in contact with a mold in which various thicknesses of polyimide (indicated by PI in the figure) are coated on the surface of the steel main mold. The change over time (calculated value) of the surface temperature is shown. As the polyimide layer covering the mold surface becomes thicker, the mold surface temperature decreases significantly.

Fig. 5 shows that a synthetic resin (rubber reinforced polystyrene) was applied to a mold with a 0.2 mm thick polyimide coated on the surface of the steel main mold at various resin temperatures and mold temperatures. The change over time (calculated value) of the mold surface temperature upon contact is shown. As the synthetic resin temperature and the mold temperature decrease, the mold surface temperature also decreases.

Fig. 6 shows a mold in which a 0.2 mm thick polyimide is coated on the mold surface of a steel main mold, and a synthetic resin (rubber reinforced polystyrene) is applied at various mold thicknesses and mold temperatures. ) Shows the change over time (calculated value) of the mold surface temperature when contacted.

Fig. 7 shows a mold in which a polyimide layer is coated on the surface of a steel main mold and a Nigel layer (indicated by N では in the figure) is coated on the surface of the mold. Using a mold with only the imid layer coated, setting the temperature of the main mold at 50 ° C, and performing injection molding with the mold at a rubber-reinforced polystyrene resin temperature of 240 ° C Temperature of the mold surface after the resin comes into contact with the outermost surface of the mold (this is the temperature of the interface between the resin surface and the nickel surface or the temperature of the interface between the resin surface and the polyimide surface) ) Shows changes over time. Figure 7 shows the change over time in the resin surface temperature when the thickness of the polyimide layer was 0.3 mm and the thickness of the nickel layer was 0.2 mm. In the figure, the solid line indicates the polyimide layer. And the nickel layer was covered, and the broken line is the case where only the polyimide layer was covered. Polyimid When the resin surface is coated, the resin surface temperature decreases with the passage of time, whereas when the polyimide layer and nickel layer are coated, the temperature drops once and then rises again and then gradually. descend. This is because the heat of the synthetic resin is absorbed by the nickel layer and lowers because the heat capacity of the surface Nigel is large. Therefore, as the thickness of the nickel layer increases, the temperature range that once decreases increases, and the temperature that increases again decreases. If the temperature of the synthetic resin is high, even if the heat is absorbed by the outermost metal layer, the heat can be supplied sufficiently. Synthetic resin temperature has a significant effect on mold surface reproducibility. FIG. 8 shows the change over time (calculated value) of the mold surface temperature when the thickness of the nickel layer coated on the polyimide layer is variously changed. We have found that the integral (Δ 型) and / or the integral (A h) need to be a certain value or more in order to improve the mold surface reproducibility in molding a synthetic resin. In FIG. 8, when the thickness of Nigel is 0.05 mm and the curing temperature of the synthetic resin is 105 ° C. (indicated by line 1 in the figure), the area 2 indicated by oblique lines is indicated by the present invention. It becomes the integral value (Δ Η). Draw a line 10 ° C below the aging temperature line 1, and the area enclosed by the line and the mold surface temperature curve becomes the integral value (A h). When the thickness of the nigel layer becomes 0.1 mm, the temperature at which the surface temperature once decreased rises again decreases, and it can be estimated that the mold surface reproducibility during injection molding becomes worse. When the thickness of the nickel layer is 0.002 mm, the resin surface temperature recovers rapidly even if it once drops, and since the temperature is high, the mold surface reproducibility during injection molding is good. In the present invention, after the heated synthetic resin comes into contact with the mold surface, while the mold surface temperature is equal to or higher than the plasticization temperature of the synthetic resin, the integral value (Δ Η ) Is 2 seconds * ° C or more, and under the molding conditions where the integrated value (A h) of the mold or (mold surface temperature-(softening temperature of synthetic resin-10 ° C))} is 10 seconds · ° C or more It is necessary to mold.

This integral value differs depending on the configuration of the mold, but also depends on factors such as the type of synthetic resin and molding conditions. This integral increases when these factors move in the next direction.

• The softening temperature of the synthetic resin decreases

• Thick insulation layer

• Thin metal layer

• Synthetic resin temperature rises • Mold temperature rises

• Thickness of molded products increases

The integral value increases in these directions, but the range that can be selected from the viewpoint of the synthetic resin to be molded, the performance of the molded article after molding, the molding cycle time, etc. is limited, and the integrated value is limited within the limited range. Select a range with a large value.

The integrated value of the present invention indicates the relationship with the mold surface reproducibility by integrating these factors.

Figures 9 to 26 show various changes in the thickness of the heat-insulating layer {polyimide (indicated by PI in the figure) or epoxy resin} and the thickness of the nickel layer on the surface of the steel main mold. The graph shows the time-dependent changes in the mold surface temperature when molding is performed by changing the thickness of the molded product, the temperature of the synthetic resin, and the temperature of the main mold. A graph showing the relationship between the integrated value of the (mold surface temperature-synthetic resin aging temperature) value Δ Η (second * ° C) (calculated value) while the mold surface temperature is equal to or higher than the curing temperature of the synthetic resin. It is. In each of these figures, the integral value of the softening temperature of each synthetic resin is the integral value (Δ 述べる) described in the present invention, and the integral value at a temperature lower by 10 ° C. than the curable temperature is the integral value described in the present invention (Δ Η). A h). The individual conditions are summarized in Tables 4 and 5, and the numbers in the figures correspond to the numbers in Tables 4 and 5.

Table 4 Molded product thickness PI thickness fii thickness ^ grease IS degree

[mm] [ma] [mm] [t] [ΐ]

HIPS 2 0.1 0.01 210 30

HIPS 2 0.1 0.02 210 30

HIPS 2 0.2 0.01 210 30

HIPS 2 0.2 0.02 210 30

HIPS 2 0.1 0.01 240 30

HIPS 2 0.1 0.02 240 30

HIPS 2 0.2 0.01 240 30

HIPS 2 0.2 0.02 240 30

HIPS 2 0.1 0.01 270 30

HIPS 2 0.1 0.02 270 30

HIPS 2 0.2 0.01 270 30

HIPS 2 0.2 0.02 270 30

HIPS 2 0.1 0.01 240 40

HIPS 2 0.1 0.01 240 50

HIPS 2 0.1 0.02 240 40

HIPS 2 0.1 0.02 240 50

HIPS 2 0.1 0.02 240 70

HIPS 2 0.2 0.01 240 50

HIPS 2 0.2 0.02 240 50

HIPS 2 0.2 0.03 240 30

HIPS 2 0.2 0.02 280 50

HIPS 2 0.1 0,03 240 .50

HIPS 2 0.2 0.03 240 50

HIPS 2 0.2 0.05 240 50

HIPS 2 0.3 0.01 240 50

HIPS 2 0.3 0.02 240 50

HIPS 2 0.3 0.03 240 50

HIPS 2 0.3 0.05 240 50

HIPS 2 0.3 0.1 210 50

HIPS 2 0.5 0.03 240 50

Figures 9 to 22 show the calculated values for PI for the heat insulation layer and rubber reinforced polystyrene (HIPS) for the synthetic resin. Figures 23 to 24 show PI for the heat insulation layer and latent heat of crystallization for the synthetic resin. a calculated for polyoxyethylene (POM), 2 5 is cross-sectional heated material canceller Mi click _{_{(Z r 0 2 / Y 2}} 0 3), from a synthetic resin! a calcd for IPS, FIG 26 is the calculated value for epoxy resin for the heat insulation layer and HIPS for the synthetic resin.

From these figures, the integrated values at the time of molding under various types of molds and various molding conditions can be seen. In other words, the calculation of the integrated value shown in the present invention requires calculation using a computer, but the approximate value of the integrated value can be easily read from the various data shown in FIGS.

In the figure, polyimide and epoxy resin are used as a heat insulating layer, and a nickel layer is used as a metal layer, but other heat-resistant polymers are used as a heat insulating material, and chromium other than nickel is used as a metal. When other metals are used, it can be inferred from the data shown in FIGS. Fig. 18 to Fig. 21 show the change of the mold surface temperature and the change of the integral value when the temperature of the synthetic resin is changed. As the temperature of the synthetic resin increases, the integral value increases significantly. In other words, heat is supplied from the synthetic resin to the heat insulating layer and the metal layer and the temperature rises, and the temperature and time for the temperature rise increase the integral value, thereby improving the mold surface reproducibility of the molded product. This is significantly different from ordinary metal molds without insulation layer coating. That is, as shown in Fig. 1, in a general metal mold, as soon as the synthetic resin comes into contact with the cooled mold surface, the synthetic resin surface layer is cooled to the same temperature as the mold temperature. The same is true even if the temperature of the synthetic resin is increased, and there is no effect of increasing the temperature of the synthetic resin. When molding with a general mold at a high synthetic resin temperature, the viscosity of the synthetic resin decreases and the transmission of the injection pressure is transmitted to the end of the molded product. However, as shown in the present invention, by increasing the mold surface temperature for a certain period of time and increasing the integral value ΔΗ and the integral value Ah, the mold surface reproducibility is not significantly improved. In the present invention, molding at a high synthetic resin temperature has the effect of significantly increasing the integral value, which is completely different from the case where a general mold is used.

In the present invention, the effect is significantly different depending on molding conditions, and it is necessary to specify at least the temperature of the synthetic resin and the temperature of the main mold. Especially, the effect of resin temperature is great. The present invention introduces the integral values ΔΗ and Δΐι, which are parameters including this factor, and clarifies the difference from the known literature.

Figure 25 shows the case of using ceramics and the case of using epoxy resin as the heat insulating material. Ceramics are introduced as heat insulating materials, but ceramics have considerably higher thermal conductivity than heat-resistant polymers, and when ceramics are used as heat insulating materials, As shown in FIG. 25, the mold surface temperature decreases rapidly, the integrated value is extremely small, and ceramics cannot be used in the present invention.

Figure 26 shows that when the thickness of the heat insulating layer becomes 0.5 mm or more, the mold surface temperature falls below the softening temperature of the synthetic resin within 5 seconds after the synthetic resin contacts the mold surface under the conditions of the present invention. It is difficult to meet the requirements.

Figure 27 shows the change in the mold surface temperature of the molding method of the present invention, and the known literature USP 538 of the reference.

8 shows the change in the mold surface temperature shown in FIG. In the reference, the mold surface temperature falls below the glass transition temperature of the synthetic resin in about 20 seconds after the synthetic resin comes into contact with the mold surface, but in the present invention, it falls below the glass transition temperature within 5 seconds. In the present invention, the molding surface temperature is reduced to a temperature equal to or lower than the curing temperature of the synthetic resin after 5 seconds, thereby shortening the molding cycle time and providing an economical molding method.

Figure 31 shows the gloss of molded products when rubber-reinforced polystyrene (Stylon 495, trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) was used and the resin temperature was changed and injection molding was performed. The glossiness used in the present invention is measured at JISK 710 and a reflection angle of 60 degrees. This gloss is a gloss based on a mirror gloss of 1.567 for the glass surface having a refractive index of 1.567, and the gloss of the synthetic resin molded article may exceed 100%. Hereinafter, the glossiness is measured by this measuring method. The gloss of the molded product changes greatly depending on the resin temperature when molded with the heat-insulating layer-coated mold compared to when molded with a general mold without the heat-insulating layer.

Figure 32 shows the relationship between the integral value (ΔΗ) and the gloss of the molded product when rubber-reinforced polystyrene (Stylon 495, trade name of Asahi Kasei Kogyo Co., Ltd.) is used. The gloss of the injection molded product depends on the injection molding speed, and the lower the injection speed, the lower the gloss. The lower the injection speed, the more remarkable the effect of the present invention is and the better the use. In the present invention, the flow velocity of the synthetic resin in the mold cavity is 20 to 300 mm Z seconds, preferably 30 to 2 mm. Molded at 0 mm / sec. The gloss value in Fig. 32 is a value obtained by injection molding at 50 mm / sec. As shown in the example of the injection molded product in FIG. 32, in the present invention, when the integral value (ΔΗ) is 2 seconds • ° C or more, the mold surface reproducibility is good, the molded product glossiness is good, and the integral value (mm When H) is 5 seconds · ° C, the glossiness is further improved, and when the integrated value (ΔΗ) is 7 seconds * ° C or more, the glossiness is nearly 100%.

Fig. 33 shows the relationship between the integral value (Δΐι) and the gloss of the injection-molded product when injection molding is performed using rubber-reinforced polystyrene (Stylon 495, trade name, manufactured by Asahi Kasei Corporation). . When the integral value (Ah) is 10 seconds · ° C or more, the mold surface reproducibility is good and the molded product gloss is good. When the integral value (Ah) is 12 seconds · or more, the glossiness is further increased. When the integrated value (Δ ΐι) becomes 15 seconds or more, the glossiness becomes almost 100%.

An object of the present invention is to obtain a molded article of high gloss having a rubber gloss of 80% or more, preferably 90% or more, and more preferably 95% or more in the rubber-reinforced polystyrene shown in the figure. This type of appearance is required to eliminate the need to paint on molded products and to use them in applications that require an appearance. Of course, if the integrated value (ΔΗ) is less than 2 seconds · ° C or the integrated value (A h) is not more than 10 seconds · ° C, the glossiness will be improved accordingly, In order to obtain a molded product with very small well-lined appearance, the integral value (ΔΗ) must be at least 2 seconds * ° C and / or the integral value (Ah) must be at least 10 seconds * ° C. It is important. We have found that the glossiness of a molded article can be arranged by the integral value (ΔΗ) and / or the integral value (Δίι) shown in the present invention, and have reached the present invention. A molded article with a good appearance can be obtained by increasing the thickness of the heat-insulating layer. However, increasing the thickness of the heat-insulating layer increases the molding cycle time and is not suitable in terms of molding efficiency. In the present invention, this is a method for achieving both improvement in appearance and molding cycle time.

Figure 34 uses a normal metal mold that does not cover the heat-insulating layer, makes the mold surface that makes up the mold cavity mirror-like, and uses rubber-reinforced polystyrene (Stylon 495, vicat The figure shows the relationship between the mold temperature and the gloss of the molded product when injection molding is performed at a temperature of 105 ° C). The mold surface reproducibility during molding can be determined from the gloss of the molded product. The mold surface reproducibility, that is, the gloss of the molded product, varies depending on the injection speed of the synthetic resin (the flow speed of the synthetic resin in the mold). However, when the mold temperature becomes (synthetic resin 钦 temp. Related to Almost constant. The higher the mold temperature, the higher the gloss of the molded product.However, to achieve a gloss of nearly 100%, the mold temperature should be close to the curing temperature of the synthetic resin to be molded. I need to raise it. However, as can be seen in Fig. 34, if the mold temperature is raised to 95 ° C, which is a temperature that is 10 ° C lower than the synthetic resin softening temperature of 105 ° C, the gloss of the molded product will be considerably improved. However, the glossiness can be said to be close to 95%, which is a class A surface. Even if the integral value (ΔΗ) is small, if the integral value (Δh) is extremely large, the mold surface reproducibility will be similarly improved. (Integral value (A h) Integral value (Δ})} The ratio tends to increase as the adiabatic layer becomes thicker. Thus, both the integral value (Δ で) and the integral value (A h) The reason why we chose these two types of integral values as a parameter was that we found that the actual result could be satisfactorily organized. For synthetic resins that are relative in nature and have a very poor appearance, or that do not have a good appearance, the value of high gloss is relatively low and molding using conventional dies If the appearance is remarkably improved as compared with the article, the article is a high gloss molded article according to the present invention.

FIG. 35 shows a state in which the interface between the heat insulating layer and the metal layer of the mold described in the present invention is finely uneven and closely adhered. It is preferable that the adhesion between the heat insulating layer and the metal layer is also large, and it is preferable that the heat insulating layer and the metal layer intersect at the interface alternately to increase the adhesion due to the anchor effect. The preferred degree of fine unevenness is a standard length of 80 m, with the average of the peaks from the highest to the fifth at the interface between the metal layer and the heat insulation layer and the average of the valley bottom from the deepest to the fifth. Is 0.5 to 10 m. Since the unevenness described here is a shape that alternately and intricately interlocks and acts as an anchor effect, and is not a simple unevenness, the elevation where the deepest of each unevenness enters is selected.

FIGS. 36 and 37 show that the method of the present invention is suitable for molding lenticular lenses and Fresnel lenses. Figure 36 shows a conventional Fresnel lens mold that has been injection molded under normal molding conditions. In FIG. 36, the mold surface of the metal mold 3 has a convex corner 5 and a concave corner 6, and the injected synthetic resin 4 generally enters the corner 7 of the concave corner 6 sufficiently. It is impossible to obtain a lens whose corners are sufficiently reproduced.

FIG. 37 shows a Fresnel lens mold formed by the method of the present invention. In FIG. 37, the main mold 8 has a heat insulating layer 9 on its surface, and further has a Fresnel lens-shaped metal layer 10 on its surface. There is. As shown in the figure, the mold surface reproducibility of ordinary Fresnel lens molds is particularly poor at the concave corners 6, and the effect of the heat insulating layer 9 is to improve the mold surface reproducibility of the concave corners 6. is there. Therefore, in the present invention, in the mold for forming the Fresnel lens or the lenticular lens, the thickness 12 of the thin portion is used as the thickness of the metal layer. The thickness of the metal layer 12 is 1 to 3 or less, preferably 15 or less of the thickness 11 of the heat insulating layer, and is 0.001 to 0.1 mm, and the metal layer is in close contact with the heat insulating layer. There is a need.

The present invention has excellent scratch resistance, in which a metal layer surface or a part of the metal layer surface is molded using a mold having an matte surface which is formed by multi-stage sand blasting and / or multi-stage etching. This is a molding method for molded articles with a fine uneven surface and an erasable surface.

Fig. 38 shows a saturated molded product (38-1) with excellent scratch resistance produced by the molding method of the present invention, and an easily matted glossy molded product (38-8) formed by the conventional method. ) Shows the cross section. In the molded article molded by the method of the present invention shown in (38-1), the tip 15 of the concave portion on the fine uneven surface of the synthetic resin molded article 13 has an acute angle, while the tip 14 of the convex portion is rounded. It is hard to be scratched. On the other hand, in the conventional molded product shown in (3 8-2), both the tips 16 and 15 of the concave and convex portions are acute angles, and when the surface of the molded product is rubbed with human nails etc. The tip of the projection is easily scraped off and easily scratched. The present invention is a method of molding a molded article shown in FIG. 38- 1, in which the ratio of the sharp end of the convex portion is small, so that it is difficult for the nail or the like to be scratched.

This will be described in more detail with an example of an injection molded product shown in FIG. In FIG. 39, the synthetic resin injected from the gate 17 flows around the hole 18 and merges at the weld to form a weld line 19. In Fig. 39, when injection molding is performed with a mold in which a mold surface is covered with a heat insulating layer and a metal layer having a fine uneven surface on the surface, the fine uneven surface of the metal layer is transferred to the molded product surface. . However, when injection molding is performed using a heat-insulating layer-coated mold with fine irregularities formed by the sand blast method, which is generally used for saturation, the area from the weld portion of the molded product 20 to the resin flow edge (hereinafter referred to as the drawing) (In the description used, this is abbreviated as “weld part 21”.) The degree of fine irregularities increases, and when molded with black colored resin, the well part 21 becomes blackish and the general part 22 becomes white-white. It is difficult to obtain a molded article having a uniform glossiness as described in the invention. The cause is estimated as follows. So The cause of this will be described with reference to FIGS. 40 and 41.

In the injection molding of the molded article shown in FIG. 39, the pressure applied to the mold wall of the elbow section 21 and the general section 22 is modeled in FIG. In FIG. 40, the pressure applied to the general part 22 of the molded article is represented by a curve 23, and the pressure applied to the elbow part 21 is represented by a curve 24. Curve 25 is the pressure applied to the gate. That is, while the pressure applied to the general portion 22 gradually increases with the elapse of the ejection time, the pressure applied to the weld portion 21 is high at the same time when the synthetic resin comes into contact with the mold wall surface. As shown in Fig. 8, the heated synthetic resin contacts the mold wall surface of the heat-insulating layer, heats the surface of the heat-insulating layer coating, and immediately starts cooling. In the mold shown in FIG. 8 in which Ni is coated to a thickness of 0.05 mm, the mold surface drops to 105 ° C. or less after 1.5 seconds. In order to reproduce the mold surface better, high pressure is applied to the resin at the same time that the heated synthetic resin comes into contact with the mold wall surface, that is, high pressure is applied to the resin while the mold wall surface and the surface layer of the synthetic resin are hot. This is preferred. As shown in FIG. 40, in the ゥ eld portion, a high pressure is applied to the resin at the same time when the synthetic resin comes into contact with the mold wall surface, and the fine irregularities on the mold wall surface are more accurately reproduced.

Fig. 41 explains this process in model form. In 4 1 1, the mold surface is composed of a heat insulating layer 26 and a metal layer 27 having fine irregularities on the surface thereof. The fine irregularities on the surface include a concave part 28 at an acute angle. When injection molding is performed with this mold, the resin pressure gradually rises after the synthetic resin 29 comes into contact with the mold wall surface in the general part of the molded product, so that the mold wall surface and the surface layer of the resin cool while the pressure rises. However, a part 30 that cannot be filled to the depth of the fine irregularities on the mold wall and is not filled occurs (4 1 1 2). On the other hand, in the peg portion of the molded product, the synthetic resin 29 comes into contact with the mold wall surface and at the same time the resin pressure rises, so that the synthetic resin can penetrate deep into the fine irregularities of the mold (4113). As a result, in the weld portion 21, the degree of surface unevenness of the molded product becomes larger than that in the general portion 22, and in the black colored synthetic resin, the weld portion becomes blackish and does not have a uniform matte state.

Such a phenomenon is remarkable when an opaque molded article is injection-molded with a mold coated with a heat insulating layer. The present invention provides a method for molding a molded article in which this defective phenomenon is improved. In order to make the surface irregularities of the elbow part and the general part of the molded product uniform, it is necessary to make the fine irregularities on the surface of the heat insulating layer an appropriate irregular shape. Although the present invention has been described with reference to a molded article having a simple shape as shown in FIG. 39, the housing and the like of a weak electric device have a complicated shape formed by a multipoint gate. In addition, in such a molded article having a complicated shape, in addition to the difference in the degree of glossiness between the general part and the ゥ eld part, there is often a difference in the degree of elimination of tuna on the left and right across the ゥ eldrain.差 The difference between the left and right across the Eldrain occurs when the flow velocity of the left and right resins is different. Resin on the side with the higher flow velocity is quickly applied with resin pressure after contacting the mold wall surface, and resin on the slower side is applied with the resin pressure slowly after contacting the mold wall surface, and there is a tendency for difference in mold surface reproducibility between left and right . The present invention is particularly effective in such a case.

FIG. 42, FIG. 43, FIG. 44 and FIG. 45 show preferred examples of the method of manufacturing the mold used in the method of the present invention. In FIG. 42, on the surface of the main metal mold 32 made of metal, there is a heat insulating layer 26 having a thickness of 0.05 to 2.0 mm, on which a thin metal layer for strengthening adhesion is provided. , And the surface is covered with two metal layers 33, 34. Since the thin metal layer for strengthening the adhesion between the heat insulating layer and the metal layer is much thinner than the metal layers 33 and 34, it is omitted in FIGS. 42 to 45. The total thickness of all the metal layers including the metal layers 33 and 34 is 1/3 or less of the thickness of the heat insulating layer 26 and is 0.01 to 0.5 mm. The metal layer provided on the thin metal layer for strengthening the adhesion between the heat insulation layer and the metal layer consists of two layers, and the thickness of the surface metal layer 34 may be 12 or more of the total metal layer. Preferably, more preferably more than 2/3. The preferred thickness of the inner metal layer 33 is 0.002 to 0.1 mm, more preferably 0.03 to 0.05 mm. The etching rate of the surface metal layer 22 is at least twice, preferably at least three times, and more preferably at least five times the inner metal layer 33. The mold is etched and the surface metal layer 2 is selectively etched mainly to obtain the mold required by the present invention shown in (42-2).

FIGS. 43 and 44 show in more detail the method of making the surface metal layer of the mold into an erased state required by the present invention by etching treatment. In FIG. 43, the mold wall forming the mold cavity of the main mold 32 made of metal is covered with the heat insulating layer 26 (43-1). Next, a thin metal layer (omitted in the figure) and two metal layers 35 and 36 are coated on the surface of the heat insulating layer 26 (43-2). In the metal layer, the etching speed of the surface metal layer 36 is preferably at least twice the etching speed of the inner metal layer 35, more preferably at least three times, and most preferably at least five times. The surface of the metal layer 36 is coated with a photosensitive resin 37 (43-3). Next, masking is performed with a mask sheet 38. Ultraviolet irradiation is performed to cure the exposed portion of the photosensitive resin (43-3-4). Next, the uncured portion of the photosensitive resin is washed away and removed, leaving a patterned cured resin 39 (43-5). Next, the metal layer in the portion not covered with the cured resin 39 is dissolved by the etching treatment to obtain a mold surface having the metal layer 36 having an uneven surface (43-6). Further, the steps from coating of the photosensitive resin (43-3) to etching (43-6) are repeated.

Figure 44 shows the second and subsequent multi-stage etching processes. In FIG. 44, a photosensitive resin 37 is coated on the surface metal layer 26 (44-1) that has been roughened by the first-stage etching (44-1-2), and pattern masking is performed on the surface. After exposing, developing, and cleaning (44-3-1), etching is performed to make the surface more uneven (44--14), and further (44-1-2) to (444--4) The process is repeated to obtain the mold (444-5) required by the present invention. The etching collides with the inner metal layer 35 having excellent etching resistance, so that the etching speed is slowed, the bottom of the concave portion of the metal layer is rounded, and no sharp-angled concave portion is formed. By injection molding using the mold shown in (44-5), a molded product excellent in scratch resistance required by the present invention shown in Fig. (38-1) can be obtained.

FIGS. 43 and 44 show a method in which a photosensitive resin is applied to the entire surface of the mold and exposed by covering with a masking film. FIG. 45 shows a more excellent method. In FIG. 45, the photosensitive resin is finely applied at intervals so as to be sprinkled on the surface of the metal layer, and is cured by irradiating it with ultraviolet light (45-1). The surface is roughened (45-2). This sprinkling application of the photosensitive resin, ultraviolet irradiation (45-3) and etching (45-4) are repeated, and this process is repeated several times to obtain the matte surface mold required by the present invention ( 4 5— 5). In the present invention, the steps from the application of the photosensitive resin to the etching are repeated preferably 3 to 10 times, more preferably 4 to 8 times, to obtain a fine irregular surface having a preferable shape. The provision of a thin corrosion-resistant metal layer that does not significantly change the shape of the fine irregularities on the surface of the mold with a matte surface with fine irregularities obtained by the multi-stage etching treatment of the present invention is not limited to durability during injection molding. It is effective for improving the performance and is included in the present invention.

The following examples and comparative examples further illustrate the present invention. In the examples and comparative examples, the following main mold, heat insulating layer, metal layer and synthetic resin were used.

Main mold: Steel (S55C) mold for injection molding. Mold thermal expansion coefficient of 1. a ^{1 X 1 0- 3 / ° C} . The molded product 20 has the mold cavities shown in FIG. The molded product has a size of 10 O mm x 10 O mm and a thickness of 2 mm, and has a hole 4 of 30 mm 3 O mm in the center. The gate 17 is a side gate as shown in FIG. 39, and a weld line 19 occurs in the molded product 20. The mold surface is mirror-like. Nineteen nests forming the mold cavity of this main mold are prepared, and hard chrome plating is performed on the surface of each nest forming the mold cavity.

Heat insulation layer A: Primer treatment is applied to the nest surface of the main mold. As a primer, a polyimide precursor solution having a high C0 group content is applied to a thin layer, and heated to form a polyimide thin layer, which is used as a primer. Then, a polyimide varnish (Trenice # 3000, manufactured by Toray Industries, Inc.) is applied, heated at 160 ° C., and the application and heating are repeated to a predetermined thickness. It is heated to 900 to make it 100% imidized, and a polyimide layer having a predetermined thickness is formed. The adhesion of the polyimide layer to the main mold is 1 kg / 10 mm.

Heat insulation layer B: Primer treatment is applied to the nest surface of the main mold. As a primer, a polyimide precursor solution having a high C0 group content is applied to a thin layer, and heated to form a polyimide thin layer to be a primer. Then, a polyimide varnish (Trenice # 3000, manufactured by Toray Industries, Inc.) is applied and heated at 160 ° C. Then, the application and heating are repeated to a predetermined thickness. Then, a thin layer of a blended polyamide varnish obtained by blending 20% by weight of a titanium oxide fine powder having an average particle diameter of 0.1 at a solid content ratio and sufficiently kneading is applied to the outermost surface of the heat insulating layer, and then coated. Heat to 290 ° C. to make 100% imidation, and form a polyimide layer of a predetermined thickness having a blended polyimide layer of 10 m thickness on the outermost surface. The adhesion of the polyimide layer to the main mold is 1 kgZ10 mm. The surface of the heat insulating layer of the metal layer A is etched with a strong acid solution containing chromic acid, then processed in the order of neutralization → sensitization processing—activation processing, and then sodium hypophosphite is used as a reducing agent. Chemical nickel plating with a phosphorus content of 3 to 4% by weight formed by chemical nickel plating at a low temperature, in a weakly alkaline state, and at a low speed. Metal layer B: A chemical nickel plating having a phosphorus content of 6 to 7% by weight, formed by performing a chemical nickel plating at 60 ° C and in an acidic condition using sodium hypophosphite as a reducing agent.

Metal layer C: Electrolytic nickel plating with a sulfur content of 0.05% by weight.

Thermal expansion coefficient of each Nikkerume luck layer of the are all nearly 1. 3 X 1 0 - a ⁵ Z ° C.

Metal layer D: Hard chrome plating. The surface hardness of this plating is HV100.

Synthetic resin for injection molding:

(a): Rubber-reinforced polystyrene (Stylon 495, trade name, manufactured by Asahi Kasei Corporation), glass transition temperature: 105 ° C.

(b): 30% by weight of glass fiber blended styrene-acrylonitrile copolymer tree B (Styrac-AS GFR 160 T, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name). The vitrification temperature of the base resin is 110 ° (: The glass fiber in the synthetic resin is E-glass and its hardness is HV640.

(c): Styrene-acrylonitrile copolymer resin (Styrac—AS 767 Asahi Kasei Kogyo Co., Ltd.). Vicat curing temperature 110 ° C.

Injection molding conditions: shown in Table 6. The flow rate of the resin in the mold is 50 mm / sec when not specified.

Gloss measurement method: JISK 710, reflection angle 60 °.

(Examples 1 to 7 and Comparative Examples 1 to 7)

A 0.05 mm thick metal layer Α is coated on the surface of the heat insulating layer of the main mold coated with the heat insulating layer Β, and a metal layer C is coated on the surface. Then, molds having a heat insulating layer having thicknesses of polyimide (PI) and nickel (Ni) shown in Table 6 are prepared. The adhesive force between the metal layer and the heat insulating layer and the adhesive force between the heat insulating layer and the main mold are each 0.5 kg / 10 mm or more. Using this mold, injection molding of the synthetic resin (a) is performed under the molding conditions shown in Table 6. Table 6 shows the integrated value of each molding condition and the glossiness of the molded product. Table 6

In Examples 1 to 7, the integrated value (ΔΗ) is 2 seconds · ° C or more, and / or the integrated value (A h) is 10 seconds' ° C or more. Further, the mold surface temperature after 5 seconds from contact with the mold surface is lower than (the aging temperature of the synthetic resin is lower than 20 ° C.) in each of the examples. The gloss of each molded product of the example is high, the well line is not conspicuous, the molded product is excellent in appearance, and can be said to be class A surface. Even if injection molding is performed 10,000 times with the mold of Example 3, separation of the heat insulating layer and the metal layer does not occur. A cross-sectional view of the bonding interface between the heat insulating layer and the metal layer in Example 3 is shown in FIG. The metal layer and the cross-section layer are in close contact at the interface of fine irregularities, and the anchor effect works.

(Example 8)

The outermost metal layer C of the mold shown in Example 7 is etched to form a leather grain-shaped pattern grain having a depth of 0.02 mm. On the surface of the metal layer, the convex portions of the pattern grain are mirror surfaces, and the concave portions are matte surfaces. Injection molding was performed using this mold in the same manner as in Example 7, and the pattern with excellent appearance was less noticeable in the well line. A molded article with a grain-like surface is obtained. The integral value (△ H) of the protrusion on the surface of the leather grain-like metal layer is 7.2 seconds · ° C as in Example 7, and the integral value (Ah) is 17 seconds ·. The mold surface temperature after 5 seconds from the contact of the synthetic resin with the mold surface has fallen below (the curing temperature of the synthetic resin minus 20 ° C).

(Example 9)

A 0.5- / m-thick metal layer A is coated on the heat-insulating layer surface of the main mold coated with a 0.3-mm heat-insulating layer B, and a 10-m metal layer B is coated on the surface, and the surface is polished. After that, a mold coated with a heat insulating layer coated with a metal layer D of 10 m is used. The adhesive force between the metal layer and the heat insulating layer and the adhesive force between the heat insulating layer and the main mold are all 0.5 kgZ10 mm or more. Synthetic resin (b) is subjected to injection molding at a resin temperature of 240 ° C and a main mold temperature of 5 (TC. After the heated synthetic resin comes into contact with the mold surface, the mold surface temperature is higher than the curing temperature of the synthetic resin. The integrated value (mH) of the value between the (surface temperature and the plasticization temperature of the synthetic resin) is at least 5 seconds * The mold surface is damaged by 100 times injection molding of the synthetic resin The mold surface reproducibility of the molded product is good, and a molded product with high gloss and less noticeable eld line is obtained.The mold surface temperature after 5 seconds from the contact of the synthetic resin with the mold surface is as follows. Softening temperature has fallen below 20 ^eC ).

(Comparative Example 8)

The main mold is coated with a 0.3 mm heat insulation layer A and the surface is polished to a mirror-like heat insulation layer covered mold. Injection molding is performed in the order of synthetic resin (c) and (b). The molding conditions are a resin temperature of 240 ° C and a main mold temperature of 50 ° C. The surface of the heat-insulating layer is not scratched by the injection molding of the synthetic resin (c) 100 times, but the surface of the heat-insulating layer is injection-molded by the synthetic resin (b) 100 times, and the gloss is high. Scratches are reduced to less than 20%.

(Example 10)

A 0.05-mm-thick metal layer A is coated on the heat-insulating layer surface of the main mold coated with a 0.2-mm heat-insulating layer B, and a 0.01-mm metal layer B is coated on the surface. Then, the surface is coated with a metal layer C having a thickness of 0.03 mm. Using this mold, the saturated surface mold of the present invention is obtained by a six-stage multi-stage etching process shown in FIG. The synthetic resin (a) is subjected to injection molding using the obtained mold of the present invention. Injection molding is performed at a resin temperature of 240 ° C and a mold temperature of 40 ° C. There is no noticeable injection line of injection molded products. The surface is a uniform matte surface, its gloss is less than 20%, and there is no noticeable scratch at 1B hardness in the pencil pull test. Fig. 46 shows the uneven shape of the surface of the injection molded product. The uneven shape is measured with a surface roughness profile meter “Surfcom 570 A” of Tokyo Seimitsu Co., Ltd. The uneven shape of the surface of the injection molded product is a surface shape that has few sharp projections protruding on the surface and is hardly damaged.

On the other hand, the case where the surface of the polyimide-coated mold of the main mold coated with 0.2 mm of the heat insulating layer A is subjected to a one-stage sandblast treatment to form an abalone-like surface is shown below.

Injection molding of a synthetic resin is performed in the same manner using the mold coated with polyimide having the fine surface unevenness. The dent of the ゥ eldrain of the molded product is 1 m or less, and the ドライ eldrain is not conspicuous, but there is a difference in the degree of glossiness of the general part 22 and the weld part 21, resulting in a uniform fungus-colored molded article. hard. Figure 47 shows the surface unevenness pattern. The surface unevenness pattern of polyimide coated mold is 47-1, the surface unevenness pattern of the general part of the molded product is 47-12, and the surface unevenness pattern of the welded part 5 of the molded product is 47-3. Show. The general part 22 and the weld part 21 of the molded product are clearly different in the surface unevenness pattern.艷 The glossy surface of the eld part 2 1 is easily scratched due to the pencil hardness test 2B hardness. Industrial applicability

By performing injection molding or blow molding of a synthetic resin using the heat-insulating layer-coated mold of the present invention, a molded article having a good appearance is obtained. Various injection molded products, such as housings of light electrical equipment and office equipment, which conventionally required a number of well-lines and required post-processing such as painting, were molded using the molding method of the present invention to improve mold surface reproducibility. In addition, the well line is less noticeable and post-processing such as painting can be omitted, which is economically effective. By omitting painting, it is easier to recycle synthetic resin, eliminating organic solvents that scatter into the air during painting, and contributing to environmental conservation.

In addition, by molding a crystalline synthetic resin by the method of the present invention, a molded article crystallized immediately before the surface of the molded article can be economically obtained. Molded products crystallized to near the surface have excellent surface hardness, wear resistance, and adhesion.

Claims

The scope of the claims

1. In the molding method of synthetic resin,

(1) On the surface of the mold that constitutes the mold cavity of the main mold made of metal, there is a heat insulating layer of less than 0.5 mm, which exceeds 0.1111111 and is made of a heat-resistant polymer adhered to the mold surface, And using a heat-insulating-layer-coated mold in which a metal layer in close contact with the heat-insulating layer is present,

(2) After the synthetic resin to be molded comes into contact with the mold surface, while the mold surface temperature is equal to or higher than the plasticization temperature of the synthetic resin, the integrated value (ΔΗ) of the value of (mold surface temperature-plasticization temperature of the synthetic resin) is 2 seconds

• Molding conditions of more than ° C and / or while the mold surface temperature is (Synthetic resin softening temperature-10 ° C) or more (Mold surface temperature-(Synthetic resin softening temperature-10 ° C) } Integral value

(A h) is more than 10 seconds

2. In the injection molding method of synthetic resin,

(1) A heat insulating layer of more than 0.1 mm and less than 0.5 mm made of a heat-resistant polymer adhered to the mold surface is present on the mold surface constituting the mold cavity of the metal main mold, and Using a heat-insulating-layer-coated mold having a metal layer with a thickness of 13 to 13 mm or less on the heat-insulating layer, and a thickness of 0.001 to 0.1 mm,

(2) Molding conditions in which the temperature of the main mold is 15 ° C or more and 100 ° C or less and the synthetic resin is set to a temperature equal to or less than 2 (TC minus the curing temperature,

(3) After the synthetic resin to be molded comes into contact with the mold surface, the integral value (Δ （) of the value of (mold surface temperature-synthetic resin's curing temperature) while the mold surface temperature is equal to or higher than the curing temperature of the synthetic resin is obtained. 2 seconds

• Molding conditions of more than ° C, and Z or while the mold surface temperature is (Synthetic resin tempering temperature-10 ° C) or more (Mold surface temperature-(Softening temperature of synthetic resin-10 ° C) )} Molding conditions where the integrated value (Δh) of the value is 10 seconds · ° C or more,

3. In the injection molding method of synthetic resin,

(1) Close contact with the surface of the mold that constitutes the mold cavity of the main mold made of metal A heat-insulating layer having a thickness exceeding 0.1 and less than 0.5 mm, which is made of a heat-resistant polymer, and a metal layer having a thickness of 13 or less on the heat-insulating layer, and 0.01 to 0.1 mm, the depth of the recess is 0.01 to 0.09 mm, and a metal layer having a grain-like surface smaller than the thickness of the projection exists. Using a layer coating mold,

(2) Molding conditions in which the main mold temperature is set to 15 ° C or higher and 100 ° C or lower and a temperature equal to or lower than the curing temperature of synthetic resin minus 20 ° C,

(3) After the synthetic resin to be molded comes into contact with the mold surface, while the mold surface temperature is equal to or higher than the softening temperature of the synthetic resin, the integral value (ΔΗ) of (the mold surface temperature minus the softening temperature of the synthetic resin) is 2 Molding conditions of seconds · ° C or more, and / or while the mold surface temperature is (synthetic resin softening temperature-10 ° C) or more, the (mold surface temperature-(softening temperature of synthetic resin-10 ° C) )} Molding conditions where the integrated value (A h) of the value is more than 10 seconds ·

4. The thickness of the heat insulation layer is more than 0.1 mm and less than 0.4 mm, the thickness of the metal layer is 13 or less of the thickness of the heat insulation layer, and 0.01 to 0.07 mm. , The integral value (ΔΗ) is 2 seconds or more and 50 seconds or less, and the or the integral value (Δh) is 10 seconds · ° C or more and 100 seconds or less * ° C and synthetic resin 5 minutes after contact with the mold surface, the injection molding is carried out under molding conditions in which the mold surface temperature has decreased to (the softening temperature of the synthetic resin −10 ° C.) or less. Injection molding method.

5. The thickness of the heat insulation layer is more than 0.12 mm and less than 0.3 mm, and the thickness of the metal layer is 1 Z5 or less of the heat insulation layer, 1 Z100 or more, and 0.02 to 0.06 mm and the integral value (ΔΗ) is 5 seconds or more and 40 seconds or less and ° C, and the integrated value (Δΐι) is 12 seconds or more and ° C or more and 70 seconds 5 ° C after the synthetic resin comes into contact with the surface of the mold and the mold surface temperature drops to (the temperature of the synthetic resin minus 10 ° C) 5 ° C or less. An injection molding method of the synthetic resin according to claim 2.

6. When the thickness of the heat insulation layer is more than 0.1 mm and less than 0.4 mm, the thickness of the metal layer at the protrusion is 1/3 or less of the thickness of the heat insulation layer, and the thickness is between 0.01 and 0.07 mm. Yes, the depth of the grain-shaped recess is 0.005 to 0.06 mm, and the integral value (ΔΗ) is 2 seconds. C or more 5 0 seconds · ° C or less, and Z or integrated value (Δh) is 10 seconds ·. (: More than 100 seconds .. (and less than 5 seconds after the synthetic resin comes into contact with the mold surface, the mold surface temperature drops below (the softening temperature of the synthetic resin-10 ° C) or less) The injection molding method for a synthetic resin according to claim 3, wherein the injection molding is performed under certain molding conditions.

7. The thickness of the heat insulating layer is more than 0.12 and less than 0.3 mm, and the thickness of the metal layer at the protrusion is 1-5 or less of the thickness of the heat insulating layer, and it is between 0.01 and 0.06 mm. Yes, the depth of the grain-shaped recess is 0.005 to 0.04 mm, and the integrated value (ΔH) is 5 seconds · ° C or more and 40 seconds or less, and / or the integrated value (Δh) 5 seconds after the synthetic resin comes into contact with the mold surface, and the mold surface temperature falls below (the synthetic resin's curing temperature-10 ° C). The injection molding method for a synthetic resin according to claim 3, wherein the injection molding is performed under reduced molding conditions.

8. The injection molding method for a synthetic resin according to claim 2, 3, 4, 5, 6, or 7, wherein the synthetic resin is injection-molded at an average flow velocity in a mold of 20 to 300 mmZ seconds.

9. In the blow molding method of synthetic resin,

(1) A heat insulating layer of more than 0.1 mm and less than 0.5 mm made of a heat-resistant polymer adhered to the mold surface is present on the mold surface constituting the mold cavity of the metal main mold, and Using a heat-insulating layer-coated mold having a metal layer with a thickness of 13 to 13 mm or less of the heat-insulating layer and a thickness of 0.02 to 0.1 mm on the heat-insulating layer,

(2) Molding conditions in which the temperature of the main mold is set to not less than 15 ° C and not more than 100 ° C, and not more than a temperature obtained by subtracting 20 ° C from the softening temperature of the synthetic resin,

(3) After the synthetic resin to be molded comes into contact with the mold surface, the integral value (Δ （) of the value of (mold surface temperature-synthetic resin's curing temperature) while the mold surface temperature is equal to or higher than the curing temperature of the synthetic resin is obtained. Molding conditions of 10 seconds or more and 200 seconds or less, and Z or while the mold surface temperature is (softening temperature of synthetic resin-10 ° C) or more, {mold surface temperature-(synthetic resin The integrated value (A h) of the temperature is 20 seconds · ° C or more and 400 seconds · The following molding conditions,

1 0. The thickness of the heat insulation layer is 0.2 mm or more and less than 0.5 mm, and the thickness of the metal layer is The thickness of the thermal layer is 15 or less 1/100 or more, and 0.04 to 0.06 mm, and the integral value (ΔΗ) is 20 seconds or more than ° C and 100 seconds or more. The blow molding method for a synthetic resin according to claim 9, wherein the blow molding is performed under the following molding conditions in which and / or the integral value (Δΐι) is 30 seconds or more and 300 seconds or less.

1 1. In synthetic resin blow molding,

(1) On the surface of the mold constituting the mold cavity of the main mold made of metal, there is a heat insulation layer of more than 0.1 mm and less than 0.5 mm made of a heat-resistant polymer adhered to the mold surface, Further, on the heat insulating layer, the thickness of the metal layer of the convex portion is 13 or less of the thickness of the heat insulating layer, and is 0.01 to 0.1 mm, and the depth of the concave portion is 0.05 to 5 mm. Using a heat-insulating layer-coated mold with a metal layer having a grain-like surface of 0.09 mm,

(2) Main mold temperature is not less than 15 ° C and not more than 100 ° C, and from the curing temperature of synthetic resin.

Molding conditions set at a temperature of 20 ° C or less, and

(3) After the synthetic resin to be molded comes into contact with the mold surface, the integral value (Δ 値) of the value of (mold surface temperature minus synthetic resin's curing temperature) while the mold surface temperature is equal to or higher than the curing temperature of the synthetic resin Is less than 10 seconds and less than 200 seconds · ° C, and Z or while the mold surface temperature is (softening temperature of synthetic resin-10 ° C) or more, Molding temperature (10 ° C)) The integral value (Δh) of the value is 20 seconds · ° C or more and 400 seconds · ° C or less.

1 2. The thickness of the heat-insulating layer is 0.2 mm or more and less than 0.5 mm, and the thickness of the metal layer of the projection is 15 or less of the heat-insulating layer thickness, 1 Z 100 or more, and 0.0 1 to 0. 0.8 mm, the depth of the grain-shaped recess is 0.05 mm to 0.07 mm, and the integral (ΔH) force

20 seconds · ° C or more 100 seconds · ° C or less, and / or integral value (Δh) 30 seconds · ° C or more

12. The method for molding a synthetic resin according to claim 11, wherein the molding is performed under a molding condition of 300 seconds · ° C. or less.

1 3. Blow molding under the molding conditions in which the time from when the parison contacts the mold surface until the blow pressure is sufficiently applied to the inner surface of the molded product is 1 to 5 seconds. Or the blow molding method of the synthetic resin according to 12.

1 4. Claim 1, 2, 3, 4, 5, 6. The method for molding a synthetic resin according to 6, 7, 8, 9, 10, 10, 11, 12, or 13.

1 5. The heat-resistant polymer forming the heat-insulating layer is made of a linear high-molecular-weight polyimide. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 10, 11, 2. Molding method of synthetic resin described in 1, 13 or 14.

1 6. After forming the outermost surface layer of the heat insulating layer with a heat-resistant polymer containing 1 to 30% by weight of a fine powdered etching aid, the outermost surface layer of the heat insulating layer is subjected to chemical etching to obtain fine irregularities. The metal layer is formed by subjecting the surface to a chemical plating and, if necessary, performing one or more of a chemical plating and a metal plating or an electrolytic plating. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 0, 1, 1, 1, 2, 1 using a mold with a metal layer over 3 kg / 10 mm or more The molding method of the synthetic resin described in 3, 14 or 15.

1 7. The metal layer surface or a part of the metal layer surface uses a mirror-shaped mold. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 10, 11, 2. The method for molding a synthetic resin according to 2, 13, 14, 15, or 16.

1 8. The composition according to claim 1, 2, 4, 5, 5, 8, 14, 14, 15 or 16, wherein a metal layer surface or a part of the metal layer surface is a lens-shaped irregular mold. Resin molding method.

1 9. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 1 in which a metal layer surface or a part of the metal layer surface uses a mold having a finely rugged shape. The molding method of the synthetic resin according to 1, 12, 13, 14, 15, or 16.

20. Claims 1, 3, 6, 7, 8, 11, 1 and 12 using a mold in which one of the projections and depressions on the surface of the metal layer has a mirror surface and the other has a matte shape. 13. The method for molding a synthetic resin according to 13, 14, 15, or 16.

2 1. Claims 19 or 20, wherein the metal layer surface or a part of the metal layer surface uses a mold having an opaque surface formed by multi-stage sand blasting and / or multi-stage etching. Molding method of synthetic resin.

2 2. A request to use a mold in which the metal layer is a metal layer having at least two layers, wherein the surface metal layer on the mold cavity side has lower hardness and / or greater etching properties than the inner metal layer. Item 21. The method for molding a synthetic resin according to Item 21.

2 3. The mold speed of the metal layer on the cavity side of the metal layer is more than twice the etching speed of the inner metal layer, and a metal mold is used in which the above metal layer has a matte surface by multi-stage etching. A method for molding the synthetic resin according to claim 22.

2 4. Synthetic resin to be molded is polystyrene, rubber-reinforced polystyrene, styrene-acrylonitrile copolymer, ABS resin, styrene-based resin such as styrene-methyl methacrylate copolymer, or polymethyl methacrylate. Claims 1, 2, 3, 4, 5, 6, 7, 8, and 9 are non-crystalline resins selected from methacrylate resins such as relays, rubber-reinforced polymethyl methacrylate, and polycarbonate. Molding of synthetic resin described in 9, 10, 11, 12, 13, 13, 14, 15, 15, 16, 17, 18, 19, 20, 20, 21, 22, or 23 Law.

2 5. The synthetic resin is a synthetic resin containing 5 to 65% by weight of a fibrous or powdery inorganic filler, and the hardness of the metal layer on the outermost surface of the mold is determined by the inorganic filler in the synthetic resin. Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 10, 11, 12, 13, 14, 15, 15, 1 6. The method for molding a synthetic resin described in 6, 17, 18, 19, 20, 20, 21, 22, 23 or 24.

26. The method for molding a synthetic resin according to claim 25, wherein the synthetic resin is a synthetic resin containing more than 20% by weight and not more than 65% by weight of an inorganic filler.

27. The method according to claim 25, wherein the synthetic resin is a synthetic resin containing 30 to 50% by weight of an inorganic filler.