JP3449626B2 - Surface improvement resin molding method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention does not impair productivity.
In addition, for resin molded products of all shapes,
Providing a molding method capable of performing surface modification on a surface
It is. Resin products obtained by the molding method according to the present invention,
Automotive parts, electric / electronic parts, machine parts, packaging materials, Japan
In all fields where resin materials such as supplies and sundries are used
Used in [0002] 2. Description of the Related Art A molded article composed of a resin and a resin composition has a surface.
It is industrially important to add functions derived from surface affinity / hydrophobicity.
Very important. Functions derived from surface hydrophilicity / hydrophobicity
Means paintability, adhesion, printability, plating, antistatic
Functions unique to hydrophilic surfaces such as water repellency, antifouling properties,
Both functions unique to hydrophobic surfaces such as mobility and abrasion resistance
Is shown. Adds functions related to the hydrophilic-hydrophobic properties of these surfaces
As a method of improving or improving
To achieve the desired surface function in secondary processing
How to form the required surface layer
Blending methods have been proposed. [0003] Means for forming the surface layer include:
Flame treatment, plasma treatment, ozone treatment, corona
Dry method such as discharge treatment method, ultraviolet or electron beam irradiation treatment method
Surface treatment method, using mineral acids such as chromic acid mixed solution and concentrated sulfuric acid
Process, the surface modification component chemically on the surface of the molded body
Wet surface treatment method such as grafting method, and table
Primer coating method to apply surface modification layer directly, etc.
Is mentioned. However, these methods are not
However, there are the following difficulties. With dry surface treatment method
Is extremely limited in the shape of
If the treatment effect is significantly reduced over time due to subsequent leaving
And the reforming effect of the treatment is not always sufficient
Often. Besides, to use expensive processing equipment
It has disadvantages such as being economically disadvantageous. The wet processing method
Although a relatively high reforming effect can be obtained, use of harmful chemicals
Must be done and complicated processing steps are required
Therefore, it is not suitable for continuous production. Also,
As for the primer coating method,
Increased production processes including cleaning and other costs
Will be high. [0004] On the other hand, other synthetic resins or additives are used as surface modifiers.
The method of performing surface modification by blending additives is
Economical due to simple processing equipment and processing steps
It is of high value and has received particular attention in recent years. For example, poly
Improving paintability and printability of propylene (PP)
Is styrene-butadiene block copolymer, ethylene
・ Vinyl acetate copolymer, ethylene / propylene rubber, etc.
Of blending inorganic powders in addition to the polymer of
JP-A-8-213043, JP-A-61-43650
Reports), styrene-based copolymers, ethylene / vinyl acetate
Rubber-like substances such as copolymers and ethylene / propylene rubber
For adding an organic peroxide when blending
JP-A-55-50007, JP-A-56-122849
And the like are disclosed. Also, JP-A-2-102
239, JP-A-4-63817, JP-A-4
JP-A-126740, etc., surface modification in synthetic resin
Kneading agent, and the affinity between the modifier and the molded substrate is used as the driving force.
To transfer the surface modifier to the surface of the compact and perform surface modification.
A method is disclosed. However, in the above method
Even so, because of the synthetic resin and additives to be blended,
Physical properties such as stiffness and heat resistance are significantly reduced,
In addition, since the modifying effect strongly depends on the molding method, injection molding
Modification effect when applied to molding methods with short molding cycles such as
Is insufficient. [0005] DISCLOSURE OF THE INVENTION The present invention relates to a hydrophilic surface.
Polar groups (hereinafter referred to as
Below, these are collectively called surface modification components. ) The molded body
By efficiently orienting toward the surface side, the resin
Without compromising the simplicity and productivity of molding,
Resin that can perform surface modification of the molded body at the same time as the shape
The purpose of the present invention is to provide a molding method. [0006] Means for Solving the Problems Molded surface of surface modifying component
In the surface modification method applying the orientation phenomenon to the surface side,
Even with the same resin, the degree of surface property modification is large depending on the molding method
It is generally known that they differ greatly. Melt press molding
Molding resin for a relatively long time
The surface modification effect is high with the molding method that contacts the plate surface
It is easy to obtain a molded body, but this is because the molded substrate surface and surface modification
Of the surface-modifying component to the surface side using the affinity of the component as the driving force
It is considered that the alignment proceeds sufficiently. However
Excellent production efficiency, such as injection molding, using the same resin
In some cases, the molding effect is not sufficient
Many. The present inventors have investigated the cause,
The following findings were obtained. In injection molding, heat plasticization injected into a mold
The resin contacts the cooled mold wall and immediately solidifies on the contact surface.
Layer is formed and the resin injected subsequently is solidified with the solidified layer
Proceeding between the layers, at the flow front
When it reaches, it goes to the direction of the mold wall and touches the mold wall
It becomes a solidified layer. Generally, in injection molding, the molding cycle
In order to shorten the mold temperature, the mold temperature is
As low as possible as long as this is not hindered and molding defects do not occur.
Set to warm. Therefore, the molten resin came into contact with the mold
Sometimes, the solidification of the resin occurs rapidly. Rapid solidification of molten resin
Modification of the surface of the substrate
Orientation of Surface Modifiers on the Surface Side Driven by Affinity and Affinity
Does not proceed sufficiently, and the obtained molded body has a sufficient reforming effect.
Often not. Sufficient orientation of the surface modification component to the surface side
In order to proceed to
For this reason, the mold temperature and the plasticization temperature of the resin
Setting the temperature to a high temperature will increase the molding cycle
Is not preferred. This dilemma consists of two steps:
Method, using a surface modifying component with excellent thermal kinetic properties
The orientation of the surface modification component toward the surface side proceeds in a short time.
Time required for the surface alignment to proceed sufficiently
Molding time by delaying the solidification of the molten resin
I think it can be solved by combining
Can be From the above findings, the present inventors have found that thermal motility
Resin containing a surface-modifying component that is easy to orient
If molded using a specific mold, the surface side of the surface modifying component
Orientation can proceed efficiently, and resin molding
Easy processing and surface with almost no loss of productivity
Finding that reforming can be performed, and completing the present invention
I came to. That is, the present invention relates to a heat-plasticized resin.
Alternatively, supply the resin composition into the mold cavity,
In the resin molding method to obtain a molded body instead,No acid in the resin
Hydrate group, carboxyl group and its derivative group, aldehyde
Group, hydroxyl group, epoxy group, amino group, amide group, iso group
At least one selected from the group consisting of cyanate groups and -SH groups
(1) Production of synthetic resin
Sometimes copolymerizing a monomer having the component in the side chain,
(2) Surface modification to the end of molecular chain in post-polymerization treatment Quality components
(3) Solution modification or melting for synthetic resin to be introduced
The component is introduced into the molecular chain terminal or side chain by denaturation.
Or (4) the molecular chain ends or
Blend the resin with the component introduced into the side chain.
SaidA resin containing a surface modifying component, orTheSurface modification
Resin composition containing at least one kind of resin containing
20 ° C on the mold wall that forms the mold cavity of the main mold
Thermal conductivity of 0.01 cal / cm-sec- ° C or less
Lower and has excellent affinity with the surface modifying component.
It is characterized by molding using a mold coated with thermal material
Surface molding resin molding method. Surface according to the invention
The improved property is derived from the hydrophilicity of the target surface of the molded product
Surface-modifying components necessary for imparting functions
The affinity between the surface and the heat insulating material surface
Achieved by turning In the present invention, the surface modification
Because it is possible to efficiently generate the orientation of the minute,
Not only does it not impair production efficiency,
It is possible to reduce the amount of introduced reforming components
In order to be able to do so, the mechanical properties associated with the
Reduction can be reduced. The surface-modifying component in the present invention is a molded article
Required for imparting functions derived from surface hydrophilicity
It is a structural component. Here, the polar group refers to the surface of the molded product
Paintability, adhesiveness, printability, plating, antistatic
Preferred for expressing unique functions on hydrophilic surfaces
Chemical structural components, specifically, acid anhydride groups, carboxy
Group, its derivative group, aldehyde group, hydroxyl group,
Xy group, amino group, amide group, isocyanate group, -S
H groups can be mentioned. [0011] The resin used in the present invention includes a thermal motion.
Polyethylene resin containing a surface-modifying component
Polypropylene resin, polystyrene resin, polycarbonate
Nate resin, polyvinyl chloride, polyvinylidene chloride,
Polyester resin, polyether resin, polyamide
Resin, polyurethane resin, PPS resin, acrylic resin
Resin, methacrylic resin, polyacrylonitrile, AB
S resin, AS resin, styrene / butadiene block
Coalescence, ethylene / vinyl acetate copolymer, ethylene / pro
Use of synthetic resins and copolymers such as pyrene copolymers
Heat transfer, especially at the molecular chain ends or side chains.
Especially for resins containing surface-modifying components in locations with excellent mobility
It can be preferably used. The surface modification component is contained in the main chain.
Resin is poor in thermal mobility around the main chain,
Sufficient orientation of the modifying component cannot be achieved, and the effect is small.
No. In the present invention, the resin containing the surface modifying component is 1
Resin composition blended as surface modifier
Can also be preferably used. The resin used in the present invention will be described in more detail.
In short, for example, using the present invention, a resin molded article is made hydrophilic.
When imparting properties, polycarbonate resin,
Polyvinyl chloride, polyvinylidene chloride, polyester
Resin, polyamide resin, polyurethane resin, acrylic
Resin, methacrylic resin, polyacrylonitrile,
Including a polar group in the main chain such as ABS resin, AS resin, etc.
If it is a resin, use a polymerization method or post-polymerization treatment or modification.
By increasing the terminal polar group concentration by
Introduce polar groups at terminal and side chain positions with excellent molecular mobility
In this case, a favorable effect can be obtained. As a method for introducing a surface modifying component into a resin,
Has a surface modifying component in the side chain during the production of synthetic resin.
Copolymerization of the monomer that forms
Introduce surface modifying components to the ends or dissolve in synthetic resin.
To the molecular chain terminal or side chain by liquid denaturation or melt denaturation
Introduce surface modifying components or use various blending techniques.
Surface modification component at the molecular chain end or side chain
Blend the introduced resin as a surface modifier
More can be done. Surface modification component due to resin modification
When introducing, various chemical reactions can be used.
Although not particularly limited, for example, maleic anhydride
Method for reacting diamine compound with grafted resin
(JP-B-44-1540) and amino alcohol
(Japanese Patent Publication No. 44-198163)
Can be used. By using these methods
Introducing amino groups or hydroxyl groups into graft chains
Can be. In addition, these methods are applied to
Aminophenol, aminoca
Reaction of amino compounds such as rubonic acid and aminobenzoic acid
Phenolic hydroxyl group, carboxylic acid group,
And a polar group such as a benzoic acid group. Further, in the present invention, thermal motility is excellent.
Introducing a surface modifying component having a modified chemical structure,
It is particularly preferable for enhancing the surface modification effect. For example, anhydrous
Various surface modification components on maleic acid grafted resin
When reacting an amino compound having
Molecule is rigid, bulky and poor in molecular mobility like a compound
Rather than using an amino compound, an aliphatic amino compound or
For amino compounds having an alkylene oxide structure
Amino compounds with flexible molecules and large molecular mobility
It is preferable to use an object. When introducing the surface modifying component, the amount introduced
Is the minimum amount required to achieve a sufficient effect
It is desirable to introduce more than the required amount.
Properties, appearance, and mechanical properties are often greatly impaired.
It is not preferable in terms of cost. The tree used in the present invention
The functions and functions exhibited by the present invention are contained in the fat or the resin composition.
As long as the moldability and mechanical properties are not impaired.
Ingredients such as pigments, dyes, reinforcing agents, fillers, heat stabilizers,
Antioxidants, weathering agents, nucleating agents, lubricants, plasticizers, other polymers
Can be added in any manufacturing and molding process
You. [0016] Melt modification of resin or mixing of surface modifier
For kneading, single screw extruder, twin screw extruder, Banbury
Kneaders such as kissa, roll, brabender, kneader
Use is preferred in terms of manufacturing cost. Surface modifier
In blending, kneading to improve the dispersion of the surface modifier
It is preferable to select a method, usually mixing using a twin-screw extruder.
After kneading, granulation is immediately performed. Including the surface-modifying component thus obtained
Resins or resin compositions containing them are described in the present invention.
The surface is made hydrophilic by molding using
Can be obtained. In the present invention
Is coated with a heat-insulating material with excellent affinity for surface-modifying components
It is necessary to manufacture a molded body using the mold thus set. This
Here, the term “excellent in affinity” refers to the state in which the resin is plasticized by heating.
In the embodiment, the interface between the surface modifying component and the resin matrix
Rather than free energy, between the surface modifying component and the heat insulating material surface
Indicates a small heat insulating material with low interfacial free energy.
Substrate component side with the interface free energy difference as driving force
Thermal insulation material that can be transferred to the surface and oriented to the surface side
Is shown. Generally, when the surface modifying component is a polar group,
A heat insulating material having a conductive surface can be preferably used. This place
Method for evaluating surface tension using the Zisman method
Surface tension at 20 ° C is 35 mN / m or more.
It is particularly preferred to use a thermal material. Specifically, resin
Improve paintability, printability, adhesiveness, etc. for molded products
If insulation is used to coat the mold surface, polyethylene
Polyester such as lentephthalate (45mN / m)
Resin or polyimide resin (38 to 42 mN /
m) and the like are preferred. Insulation material is coated on the mold surface
After processing, physically insulate the insulating material surface
Or by performing a chemically hydrophilic treatment,
The surface tension of the material can be controlled and used.
You. The thermal conductivity of the heat insulating material used in the present invention is
It must be 0.01 cal / cm · sec · ° C or less.
It is important. Matrix for higher thermal conductivity
Table of surface modification components whose rapid solidification has good affinity with the substrate
The effect of surface modification is to prevent migration to the surface and orientation.
Fruit is not fully exhibited. However, thermal conductivity is 0.0
Use a heat insulating material of 1 cal / cm · sec · ° C or more.
In some cases, setting the mold temperature to a high
Quality effect, but can be achieved by increasing the solidification time.
This leads to a reduction in shape efficiency, which is not preferable. Scold
In addition, it shall be suitable as a heat insulating material used in the present invention.
And a resin and a ceramic. this house,
The resin material has a thermal conductivity (cal / cm · sec · ° C) of 1
0^-FourIt is particularly preferable because the heat insulating effect is large in order. C
Thermal conductivity of lamic material is slightly larger than that of resin material.
0^-3Because it is an order, it has the same heat insulation effect as a resin material
In order to be effective, the coating layer must be somewhat thicker
No. Further, the cutting of the mold according to the present invention is performed.
Thermal material is excellent in heat resistance in addition to the requirements described above
High resistance to heat and heat cycles, and excellent wear resistance
And that the mold body can be covered well,
Properties such as good adhesion and surface polishing
It is desirable that quality be provided. In addition, insulation material coating
Regarding the thickness, it is practically on the outermost layer of the mold and is a thin layer.
It is possible to suppress the increase in cooling time,
Good. The surface modification effect is fully exhibited and the molding effect
The preferred insulation material coating thickness to maintain the efficiency
Thermal conductivity of heat insulating material, resin temperature during molding, mold temperature,
Since it changes depending on molding conditions such as resin injection speed, etc.
Consider the conditions and molding cycle, etc.
Good to decide. Next, when polyimide is used as a heat insulating material,
The case is described in more detail. 20 ° C of polyimide
The surface tension is approximately 3 when fluorine atoms are not included.
It is in the range of 8 to 42 mN / m.
Orientation of functional groups to improve paintability, printability, adhesiveness, etc.
It is suitable for Use polyimide as insulation material
What is required is a mold table for complicated shapes used in injection molding etc.
It is particularly advantageous when coating surfaces. Used in the present invention
Insulation material to withstand multiple molding cycles
It is preferable that it is firmly adhered to the mold surface. That
The mold surface should be coated with a durable film that adheres the mold sufficiently.
It is desirable to coat. Polyimide for complex mold surfaces
Before polyimide to cover and tightly adhere
Polyamide acid as a precursor is dissolved in N-methylpyrrolidone or the like.
Dissolve in medium and apply to mold wall, then heat
Can be performed most preferably by the method of forming
You. The polyimide precursor polymer has a carboxyl group
Because of the polar group, it has good adhesion to the mold,
Liimide reacts to form a close contact with the mold surface
A thin polyimide layer is obtained. Also, a resin or a resin plasticized by heating
Supplying the composition into a mold and pressurizing and cooling to obtain a molded body
In the process, the mold surface reaches 100 ° C for each molding
Heating and cooling of the temperature difference are repeated. Generally with insulation materials
Since the thermal expansion coefficient of metal is very different,
Intense stress is generated at the interface with the substrate. This stress
As a heat insulating material that can withstand tens of thousands of
Strength and breaking elongation are both large, and the adhesion to metal is large
That polyimides meet these requirements.
It is convenient. Above all, adhesion to metals such as fluorine
Strong, high-molecular-weight polymer that does not contain
Liimide is most preferred. Further, in order to obtain heat resistance, the poly is used.
The glass transition temperature (Tg) of the amide is preferably higher. straight
Although the Tg of the chain polyimide varies depending on the constituent components,
Tg is preferably 200 ° C. or higher, more preferably 230 ° C.
° C or higher. The smaller the thermal conductivity of polyimide, the better
However, the thermal conductivity of polyimide is 0.002 cal / c
Those having m · sec · ° C or less can be particularly preferably used. The thickness of the polyimide layer is 0.01 to 2 mm
Moderately selected in the range. With a thickness of less than 0.01mm
Is less effective in improving the molded product surface
The cooling effect of the mold is reduced, and the molding efficiency is reduced. Mold temperature
The higher the thickness, the thicker the polyimide layer
In the range of 0.01 to 2 mm. Ma
Further, the molding method using the mold of the present invention is also preferable.
The thickness of the new polyimide layer is different. The mold of the present invention is the most
In the case of injection molding that can be used well, 0.01 to 0.5 mm
Is preferable, and more preferably 0.03 to 0.2 m
m. On the other hand, in extrusion blow molding,
A thickness of 0.1 to 1 mm is preferred. In addition, "Po
When the layer thickness is not uniform,
Means its maximum thickness. Further, the linear polymer used in the present invention
It is preferable that the strength and elongation of the polyimide are large,
Especially high elongation at break is convenient for cold and heat resistant cycle
The required elongation at break is 10% or more, preferably 2%.
0% or more. Measurement of elongation at break conforms to ASTD 638
Do it. Preferred are high molecular weight polyimides that can be used in the present invention.
As a suitable example, Kapton (trade name, manufactured by Toray Industries, Inc., Tg
= 428 ° C), Novax (trade name, Mitsubishi Kasei Corporation)
, Tg = 399 ° C), Upilex R (trade name, U
(By Kobesan Co., Ltd., Tg = 303), Upilex S
(Trade name, manufactured by Ube Industries, Ltd., Tg = 359 ° C.), La
rc TPI (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., Tg =
256 ° C.), PI2088 (manufactured by The Upjohn Co., Tg =
342 ° C.), PAI (Amoco Corp., Tg = 230)
° C). Hereinafter, preferred embodiments of the present invention will be described. (1) The surface modifying component is a polar group,
Insulation material with surface tension of 35 mN / m or more was coated
Making the surface of the molded body hydrophilic by molding using a mold
The molding method according to claim 1, wherein: (2) Before the heat-insulating material is made of linear high-molecular-weight polyimide
The molding method according to claim 1. (3) The resin or the resin composition contains a polar group-containing polyp.
One or more propylene-based resins or resins containing polar groups
The claim, wherein the polypropylene resin composition is contained.
The molding method according to 1. [0026] The present invention will be described in more detail with reference to the following examples.
You. The characteristic values were evaluated by the following methods. Water droplet contact angle measurement
Ultrasonic cleaning of the shape in ethanol for 10 minutes
After rinsing the molded body surface with clean ethanol,
Wipe off ethanol and leave at 23 ° C for 1 hour to dry
I let it. At 23 ° C., the surface of the molded body has a diameter of 1.5 to 2.
Put a drop of 0 mm distilled water gently using a syringe,
The contact angle of a water drop 10 minutes after placing the drop was measured using a contact angle meter.
(Model CA-S150, manufactured by Kyowa Interface Science Co., Ltd.)
Measurement was performed to evaluate the hydrophilicity / hydrophobicity of the surface of the molded body. Urethane
Paint adhesion test (1) Pre-processing and baking processing Cleaning the surface of the molded 2mm thick plate with ethanol
And after drying at 20 to 25 ° C. for 1 hour or more,
Urethane paint (Rethane PG80, Kansai Paint Co., Ltd.)
Spray coating (30-40 μm thickness) using
Was. Then, it was left at 20 to 25 ° C for 1 hour.
After that, bake at 100 ° C for 30 minutes in a hot-air circulation dryer.
Treatment. 24 hours after the baking process is completed
After standing for a while, the adhesion of the coating film was evaluated by a cross-cut peel test.
went. (2) Cross-cut peel test Using a cutter knife, make one parallel line perpendicular to the coating surface.
One hundred grids were drawn one by one at an interval of 1 mm.
Cellophane adhesive tape (JIS-Z1522)
Apply sufficient pressure and keep it at about 30 degrees with the coating surface.
It was peeled off, and the state of the portion surrounded by the grid was observed. result
Is represented by remaining number / 100. [0027] Examples 1-2 The amount of maleic anhydride added was 0.3 wt.
% (From titration with sodium methylate standard solution)
MFR (230 ° C, 2.16kgf) is 71g / 10m
in maleic anhydride-modified polypropylene (MPP)
Using an injection molding machine, cylinder set temperature 230 ° C, gold
Under the condition of mold setting temperature 60 ℃, each cavity mold surface
Polyimide film (trade name Kapton, Toray)
2.5 × 10 thermal conductivity^-Fourcal / cm ・ s ・
° C), polyester film (PET, trade name Lumirror, Toray)
Co., Ltd., thermal conductivity 3.6 × 10^-Fourcal / cm ・ s ・
℃) and Teflon film (Naflon, Nichias Co., Ltd.)
Made, thermal conductivity 6 × 10^-Fourcal / cm ・ s ・ ℃)
The molded product was injected into the mold to obtain a flat molded body having a thickness of 2 mm.
MPP has an acid anhydride group (polar group) at the end of the molecular chain or
Present in the graft chain. In addition, hydrocarbon chains are contained in MPP.
Terminals (hydrophobic groups) are also present. As shown in Table 1
And mold surface coated with polyimide or polyester
Surface contact of water droplets on the compact obtained using a mold
The antenna is a molded product obtained by injecting it into an unmodified mold (steel).
The contact angle was smaller than that of (Comparative Example 2).
That is, it became more hydrophilic). [0028] Comparative Examples 1 and 2 Aluminum having a thickness of 100 μm (heat transfer
A mold coated with a conductivity of 0.5 cal / cm · s · ° C.)
Examples 1 to 3 for a surface-unmodified mold (steel material)
MPP used in the above was set at a cylinder set temperature of 230 ° C and a mold.
Molded under the condition of a set temperature of 60 ° C.
When the surface contact angle of a water droplet was measured, the results shown in Table 1 were obtained.
was gotten. [0029] Embodiments 4 and 5 Nylon-6 (S.Br1242, Asahi
100 parts by weight of hexamethyle
1 part by weight of diamine, set temperature 240 ° C,
Melting using a twin-screw extruder at a screw rotation speed of 250 rpm
The amount of amino group terminal was increased by melting reaction
A nylon-6 pellet (amine-modified PA) was obtained. Get
Using the injection molding machine, the pellets
At a temperature of 250 ° C and a mold set temperature of 60 ° C,
The surface of the mold should be 50 μm thick polyimide or polyester.
Injected into a mold covered with a tool
I got As shown in Table 2, water was
The surface contact angle of the drop is determined by injection into an unmodified mold.
The contact angle was smaller than that of the body (Comparative Example 3). [0030] Comparative Example 3 Amine-modified PA pellets used in Examples 4 and 5
Set the cylinder at the cylinder set temperature using an unmodified surface mold.
Molding at a temperature of 250 ° C and a mold set temperature of 60 ° C.
Measurement of the surface contact angle of water droplets on the compact
In addition, the results shown in Table 2 were obtained. [0031] Comparative Examples 4-6 Nylon-6 (S.Br1242, Asahi
Without chemical modification of amine
Using the injection molding machine as it is, set the cylinder temperature to 25.
Cavity mold surface at 0 ° C, mold set temperature 60 ° C
Was coated with a 50 μm thick polyimide or polyester.
Injected into mold and unmodified surface mold, thickness 2m
m was obtained. As shown in Table 3, the obtained components
The surface contact angle of the water droplet on the feature is determined by the presence or absence of the mold modification material.
The values are almost the same regardless of the
I couldn't. [0032] Examples 6 and 7 The amount of maleic anhydride added was 0.5 wt.
% Of MPP with MFR of 70g / 10min by weight
To a diamine compound (Jeffamine D-400,
5 parts by weight of Mitsuishi Texaco Chemical Co., Ltd.)
At a constant temperature of 200 ° C. and a screw rotation speed of 250 rpm,
Melt kneading using a twin-screw extruder to add amino terminal
The obtained PP pellet (amine-modified PP) was obtained. Got
Pellets are formed using an injection molding machine in the same manner as in Examples 1 and 2.
Under the conditions described above. As shown in Table 4, the mold table
Mold with surface coated with polyimide or polyester
The surface contact angle of water droplets on the compact obtained using
In comparison with the molded product obtained by injection into the modified mold (Comparative Example 7)
Small contact angle. In addition, urethane-based
Spray paint and cross-cut peel off coating adhesion
When evaluated by a release test, it was determined that no
The obtained coating film adhesion was obtained. [0033] Comparative Example 7 Amine-modified PP pellet used in Examples 6 and 7
Set the cylinder at the cylinder set temperature using an unmodified surface mold.
Molding at a temperature of 230 ° C and a mold set temperature of 60 ° C.
The surface contact angle of the water droplet with respect to the molded product was measured. Ma
In addition, urethane coating was applied to the molded body in the same manner as in Examples 6 and 7.
Evaluation of film adhesion by cross-cut peel test
In addition, the results shown in Table 4 were obtained. [0034] [Embodiments 8 and 9] Echile with MFR of 25 g / 10 min
To 32 parts by weight of propylene-block copolymer (a)
MPP with an addition amount of maleic anhydride of 0.5 wt%
(B) 48 parts by weight of ethylene-propylene rubber (bis
Talon 805, manufactured by Exxon Chemical Co., Ltd.)
0 parts weight, plus talc (P-3, Nippon Talc Co., Ltd.)
), The total amount of (a), (b) and (c) being 100 weight
Parts by weight, and 25 parts by weight of the diamine compound (Jeff
Armin D-400) in a mixture of 2.4 parts by weight and twin-screw extrusion
Has amino groups by melt-kneading using a mixer
Pellets of the PP resin composition were obtained. The resulting pellet
Using an injection molding machine under the same conditions as in Examples 1 and 2.
A flat plate was obtained. As shown in Table 5, the mold surface was
Using a mold coated with imide or polyester.
The surface contact angle of the water droplet on the
Smaller than the molded product obtained by injection into the mold (Comparative Example 8)
It was the contact angle. In addition, a urethane-based paint
Play coating to improve coating adhesion in cross-cut peel test
Excellent evaluation shows that the coating film does not peel at all.
Adhesion was obtained. [0035] Comparative Example 8 Examples 8 and 9 were applied to an unmodified surface mold.
The amino group-containing PP-based resin composition used in
Set at 230 ° C setter temperature and 60 ° C set mold temperature.
Measures the surface contact angle of water droplets on the shaped body obtained
did. In addition, as in Examples 8 and 9,
Evaluate the adhesion of the urethane coating by the cross-cut peel test.
As a result, the results shown in Table 5 were obtained. [0036] [Table 1] [0037] [Table 2] [0038] [Table 3] [0039] [Table 4] [0040] [Table 5] [0041] According to the present invention, the molding efficiency is almost reduced.
Without having to, even in a molded body having a complicated shape,
The surface modification of the molded body can be performed simultaneously with the molding. Book
According to the invention, paintability, adhesiveness, printability, plating, charging
Adds unique features to hydrophilic surfaces, such as prevention, to molded products
Can be Further, the molding method of the present invention
It can be applied to any known molding processing method, for example,
Extrusion molding, compression molding, extrusion molding (sheet molding, blow molding)
Easy to mold into various shapes by shape, etc.
And a very wide variety of practically useful products
Can be made.

Continuation of front page (56) References JP-A-5-38721 (JP, A) JP-A-4-90316 (JP, A) JP-A-54-142266 (JP, A) JP-A-5-162172 (JP) JP-A-62-108919 (JP, A) JP-A-6-190833 (JP, A) JP-A-5-131456 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) B29C 45/00-45/84 B29C 33/00-33/76

Claims (1)

(57) [Claim 1] In a resin molding method in which a heat-plasticized resin or a resin composition is supplied into a mold cavity and pressurized and cooled to obtain a molded body , an acid is added to the resin. Anhydride group, carboxy
Sil group and its derivative group, aldehyde group, hydroxyl group,
Poxy group, amino group, amide group, isocyanate group,-
At least one table selected from the group consisting of SH groups
The surface-modifying component is prepared by:
(2) post-polymerization treatment of a monomer having a side chain
(3) introducing a surface modifying component at the molecular chain end
Molecular chain of synthetic resin by solution modification or melt modification
Introduce the component to the terminal or side chain, or (4)
This component is introduced to the molecular chain terminal or side chain using the
Resins containing the surface modifying component selected from, blending incoming resinous or resin containing the surface-modifying component 1
A resin composition containing at least two kinds of resin compositions having a thermal conductivity at 20 ° C. of not more than 0.01 cal / cm · sec · ° C. on a mold wall forming a mold cavity of a main mold made of metal, and a surface modifying component Molding method using a mold coated with a heat insulating material having an excellent affinity for the resin.