JP4058438B2 - Three-dimensional decorative body and method for manufacturing three-dimensional decorative body - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a three-dimensional decorative body made of a hard-to-adhere base material and a method for manufacturing the three-dimensional decorative body, and in particular, a three-dimensional decorative body made of a hard-to-adhere base material suitable for complex structures such as vehicle parts and the like. The present invention relates to a method for manufacturing a three-dimensional decorative body.

  Although hard-to-adhere materials such as silicone resin, fluororesin, polyethylene resin, and urethane resin are frequently used for vehicle parts, etc., the surface of hard-to-adhere base materials made of these hard-to-adhere materials is hydrophobic and repellent. It is often water-based, and surface treatment such as adhesion of other members, printing, and UV coating is generally difficult. In particular, when these difficult-to-adhere materials are three-dimensionally processed or foamed, the problem is that the surface structure of the difficult-to-adhesive base material becomes complicated and smooth, making it difficult to adhere to other members. It was observed.

  Therefore, as a method for modifying the surface properties of a difficult-to-adhere base material made of such a difficult-to-adhere material, a primer treatment or a silane coupling agent or a titanium coupling agent is applied to the surface. Has been done.

  However, in order to obtain a predetermined modification effect, a relatively large amount of primer, silane coupling agent, etc. are required, and not only a specific processing facility is required but also a long processing time is required. The problem of was seen.

  Therefore, as a method for modifying the surface of a hard-to-adhesive substrate in place of primer treatment or coupling agent treatment, ultraviolet irradiation method, corona discharge treatment, plasma treatment, surface sensitive group imparting method, surface photografting method, sandblasting method, solvent treatment, Various surface modification methods such as chromic acid mixture treatment have been studied.

  For example, Japanese Patent Laid-Open No. 5-68934 discloses a technique for improving the wettability and adhesion of a coating by irradiating the surface of a hydrophobic plastic with ultraviolet rays using a high pressure mercury lamp made of synthetic quartz. Yes. U.S. Pat. No. 5098618 discloses a technique for improving the wettability and adhesion of a coating by selectively irradiating ultraviolet rays having wavelengths of 185 nm and 254 nm onto the surface of a hydrophobic plastic under a mixed gas. . Japanese Patent Application Laid-Open No. 10-67869 discloses a method of performing corona treatment with a high voltage pulse while blowing a gas onto a plastic surface with poor wettability. Japanese Patent Laid-Open No. 8-109228 discloses a surface activation treatment such as ozone treatment, plasma treatment, corona treatment, high-pressure discharge treatment, and ultraviolet irradiation on the surface of polyolefin resin or the like in order to improve dyeability. Thereafter, a method of grafting a vinyl monomer is disclosed.

  However, these surface modification methods not only have insufficient surface property modification, but also require environmental problems such as contamination of the work environment and danger, water washing, and waste liquid treatment. In addition, there were also problems in the work such as, and economic problems such as large-scale and expensive equipment.

  On the other hand, as a simple and inexpensive surface modification method, it is conceivable to flame-treat the surface of a hard-to-adhere substrate, but not only the surface property modification represented by the wetting index and contact angle is insufficient. There was a problem that the effect did not last for a long time. Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 9-124810, there has been a problem that thermal deformation is likely to occur when the surface of a hardly-adhesive substrate is subjected to a flame treatment.

  Therefore, the inventors of the present invention, as disclosed in DE00100192626A1, mainly modify the surface of the solid substrate surface of a metal or glass product by at least one oxidation flame treatment, And a method of modifying the surface of the solid substrate, which includes a step of modifying the surface by one silicic acid flame treatment. According to such a method for modifying the surface of a solid substrate, the surface of the solid substrate can be surely modified, and an effect that a printing ink, an ultraviolet curable paint, or the like can be firmly bonded can be obtained.

However, since the disclosed method for modifying the surface of a solid substrate uses an alkoxysilane compound such as tetramethoxysilane (boiling point: 122 ° C.) having a high boiling point as the silane compound, a large amount of such an alkoxysilane compound is used. When mixed with air or the like, there was a phenomenon that partial incombustibility was likely to occur. In addition, since a separate oxidation flame treatment step is included before the silicic acid flame treatment, there is a problem that the treatment time is longer by that amount although a better modification effect can be obtained on the surface of the solid substrate.
Japanese Patent Laid-Open No. 5-68934 U.S. Pat. 5098618 JP-A-10-67869 JP-A-8-109228 JP-A-9-124810 DE001001926A1 publication

  Thus, as a result of diligent efforts, the inventors have made a three-dimensional processing or foaming of a hard-to-adhere base material made of a hard-to-adhere material, and even against the surface of these hard-to-adhere base materials. The inventors have found that the surface modification of the hardly-adhesive substrate can be carried out uniformly and sufficiently by performing a flame treatment derived from the fuel gas containing the silane compound, and the present invention has been completed.

  That is, the present invention provides a three-dimensional decorative body capable of firmly adhering a decorative member to a three-dimensionally processed hard-to-adhere base material and a foam layer or cushion layer (intermediate layer) thereon, and a method for manufacturing the same. Is to provide.

According to the present invention, in a three-dimensional decorative body comprising an intermediate layer and a powder slush molded decorative member on a three-dimensionally processed difficult-to-adhere substrate, the hardly adhesive substrate is an olefin resin. , A urethane resin, a fluororesin, a silicone resin, and a polyester resin, and the surface on the intermediate layer side of the hardly adhesive substrate and the surface on the decorative member side of the intermediate layer, or any of them A three-dimensional decorative body characterized in that a flame treatment derived from a fuel gas containing a silane compound having a boiling point (under atmospheric pressure) of 10 to 100 ° C. is provided on one of the surfaces. The point can be solved.

That is, the surface of the difficult-to-adhere base material is appropriately surface-modified by the silicic acid flame treatment, and the three-dimensionally processed hard-to-adhere base material and the foam layer or cushion layer (intermediate layer) thereon are decorated. The member can be firmly bonded.
Further, since the decorative member is powder slush molded, it is possible to provide a decorative member having a more excellent three-dimensional effect and a special shape.
In addition, by configuring the difficult-to-adhere base material from a predetermined resin, the decorative member can be firmly bonded at the place where the decorative member is provided, and at any place other than the place where the decorative member is provided When the base is exposed, moderate peelability can be exhibited.
Furthermore, by setting the boiling point of the silane compound to be used at 100 ° C. or lower, the decorative member can be firmly adhered to the surface of a difficult-to-adhere substrate such as silicone rubber, fluorine rubber, or foamed urethane material. it can. Further, by using such a silane compound, the surface modification effect can be maintained for a longer time.

In constituting the three-dimensional decorative body of the present invention, the intermediate layer is preferably a foam layer or a cushion layer.
By comprising in this way, the three-dimensional ornament which is more excellent in a three-dimensional effect and can express moderate cushioning properties can be provided.

Further, in constituting the three-dimensional decorative body of the present invention, the decorative member is preferably made of at least one resin of epoxy resin, vinyl chloride resin, acrylic resin, olefin resin, urethane resin, or polyester resin. .
By configuring in this way, it is possible to use a decorative member that is highly versatile, inexpensive, and excellent in decorative properties, and as a result, provides a three-dimensional decorative body that is inexpensive and excellent in decorative properties. can do.

In constituting the three-dimensional decorative body of the present invention, the silane compound is preferably at least one compound selected from the group consisting of an alkylsilane compound, an alkoxysilane compound, and a modified product thereof.
By using such a silane compound, the decorative member can be more firmly bonded to the surface of a difficult-to-adhere substrate such as silicone rubber, fluororubber, or urethane foam material. Further, by using such a silane compound, the surface modification effect can be maintained for a longer time.

Further, in constructing the three-dimensional decorative body of the present invention, the wetting index (measurement temperature 25 ° C.) of the surface of the difficult-to-adhere base material and / or the intermediate layer after the flame treatment is applied. A value within the range of 40 to 80 dyn / cm is preferable.
By comprising in this way, a decoration member can be adhere | attached over a long time very strongly.

In constructing the three-dimensional decorative body of the present invention, it may comprise at least one vehicle part selected from the group consisting of an in-front panel, a door, a chair, a console box, an interior material, a bumper and an ornament. preferable.
By comprising in this way, the three-dimensional ornament which is excellent in decorating property and shows a strong adhesive force between ornament members can be provided.

Another aspect of the present invention, on the difficult-to-bond substrates which are embossed coatings, an intermediate layer, a decorative member formed by powder slush molding in the production method of the three-dimensional decoration body provided with a flame adhesion The base material is composed of at least one of an olefin resin, a urethane resin, a fluororesin, a silicone resin, and a polyester resin, and the surface on the intermediate layer side of the hardly adhesive base material, and the decoration on the intermediate layer A process of performing a flame treatment derived from a fuel gas containing a silane compound having a boiling point (under atmospheric pressure) of 10 to 100 ° C. on the surface on the member side or one of the surfaces, and a decoration above the intermediate layer And a step of laminating the members .

  That is, when manufacturing a three-dimensional decorative body, by including a silicic acid flame treatment step, the surface of the hardly-adhesive substrate is appropriately surface-modified, and the three-dimensionally processed difficult-to-adhere substrate and the top thereof A three-dimensional decorative body in which a decorative member is firmly bonded to a foam layer or a cushion layer (intermediate layer) can be efficiently manufactured.

Moreover, when implementing the manufacturing method of the three-dimensional decoration body of this invention, it is preferable to make the temperature of a flame into the value within the range of 500-1,500 degreeC.
By carrying out in this way, it is possible to prevent incomplete combustion of the silane compound, etc., and to decorate the three-dimensionally difficult-to-adhere base material and the foam layer or cushion layer (intermediate layer) thereon. The members can be bonded extremely firmly.

  Moreover, if it is the temperature of such a flame, although it will be influenced to some extent by processing time, a deformation | transformation of a hard-to-adhere base material can be prevented effectively.

Moreover, when implementing the manufacturing method of the three-dimensional ornamental body of this invention, it is preferable to make the flame processing time into the value within the range of 0.1 second-100 second.
By carrying out in this way, it is possible to prevent incomplete combustion of the silane compound, etc., and to decorate the three-dimensionally difficult-to-adhere base material and the foam layer or cushion layer (intermediate layer) thereon. The members can be bonded extremely firmly.

  Moreover, if it is the processing time of such a flame, although it will be influenced to some extent by the temperature of a flame, a deformation | transformation of a difficult-to-adhere base material can be prevented effectively.

Further, in carrying out the method for producing a three-dimensional decorative body of the present invention, a flame treatment derived from a fuel gas containing no silane compound on the surface of the hardly adhesive substrate and the surface of the intermediate layer, or any one of the surfaces It is preferable to further include the step of performing.
By carrying out in this way, it is possible to effectively remove dust, impurities, etc. adhering to the surface of the difficult-to-adhere substrate, and to effectively exhibit the silicic acid flame treatment effect.

  Hereinafter, with reference to the drawings, preferred embodiments of the three-dimensional decorative body and the method of manufacturing the three-dimensional decorative body of the present invention will be specifically described.

[First embodiment]
As illustrated in FIG. 1, the first embodiment is a three-dimensional decorative body 10 including an intermediate layer 56 and a decorative member 54 on a three-dimensionally processed difficult-to-adhere base material 58. The surface of the adhesive substrate 58 and / or the surface of the intermediate layer 56 is subjected to a flame treatment (silicic acid flame treatment) derived from a fuel gas containing a silane compound. The decorative body 10.
That is, in a three-dimensional decorative body provided with an intermediate layer and a decorative member formed by powder slush molding on a three-dimensionally processed difficult-to-adhere substrate, the difficult-to-adhere substrate is an olefin resin, a urethane resin, It is composed of at least one of a fluororesin, a silicone resin, and a polyester resin, and the surface on the intermediate layer side in the hardly adhesive substrate and the surface on the decorative member side in the intermediate layer, or any one surface And a flame treatment derived from a fuel gas containing a silane compound having a boiling point (under atmospheric pressure) of 10 to 100 ° C.

1. Three-dimensionally processed hard-to-adhere base material (1) type The kind of hard-to-adhere base material used in the first embodiment is not particularly limited, but examples thereof include urethane resins, fluororesins, Silicone resin, polyester resin, polyethylene resin, polypropylene resin, modified polypropylene resin, polymethylpentene resin, polyester resin, polycarbonate resin, polyethersulfone resin, polyacrylic resin, polyetheretherketone resin, polyimide resin, polysulfone resin, polystyrene resin , Polyamide resin, polyphenylene sulfide resin, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride resin, tetrafluoroethylene-perfluoroether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer Polymer, polytetrafluoroethylene resin, polyvinylidene fluoride resin, polytrifluorochloroethylene resin, ethylene-trifluorochloroethylene copolymer olefin rubber, urethane rubber, fluororubber, silicone rubber, ethylene-propylene rubber, ethylene-propylene- Examples thereof include at least one selected from the group consisting of diene rubbers, styrene-based thermoplastic elastomers, and urethane-based thermoplastic elastomers.

  Out of these resins, a silicic acid flame treatment is carried out on polyethylene resins, polypropylene resins, polyester resins, polycarbonate resins, polytetrafluoroethylene resins, etc., which have a particularly large contact angle and a low wetting index, thereby making an excellent modification. A quality effect can be demonstrated.

(2) Filler It is also preferable to add a filler such as a metal material, an inorganic filler, or a fiber to the hardly adhesive substrate.
As such a metal material, one kind of aluminum, magnesium, stainless steel, nickel, chromium, tungsten, gold, copper, iron, silver, zinc, tin, lead, or a combination of two or more kinds of metal materials is preferable.

  In addition, as an inorganic filler, titanium oxide, zirconium oxide, zinc oxide, indium oxide, tin oxide, silica, talc, calcium carbonate, lime, zeolite, gold, silver, copper, zinc, nickel, tin, lead, solder, glass, A single type of ceramic or the like or a combination of two or more types is preferred.

  Furthermore, as the fiber, carbon fiber, aramid fiber, glass fiber, polyester fiber, polyamide fiber, metal fiber, ceramic fiber and the like are preferably used alone or in combination of two or more.

  In addition, when adding a metal material, an inorganic filler, or a fiber with respect to a difficult-to-adhere base material, the addition amount may be set to a value within a range of 0.01 to 80% by weight with respect to the total amount. Preferably, the value is in the range of 0.1 to 50% by weight, and more preferably in the range of 1 to 30% by weight.

(3) Form Further, the form of the hard-to-adhere base material is not particularly limited as long as it is three-dimensional. For example, a cylindrical shape, a columnar shape, a spherical shape, a block shape, a tubular shape, a pipe shape, an uneven shape, a film Shape, fiber shape, fabric shape, bundle shape and the like are preferable. 2 is installed on the front panel 101 as shown in FIG. 2, the door 102 as shown in FIG. 3, the chair 103 as shown in FIG. 4, the console box 104 as shown in FIG. 5, and the door as shown in FIG. It may be a vehicle component such as the interior material 105, the bumper 106 as shown in FIG. 7, and the ornament 107 as shown in FIG.

  Further, the hardly adhesive substrate may partially have a planar structure such as a plate shape, a sheet shape, a film shape, a tape shape, a strip shape, a panel shape, and a string shape.

  Furthermore, as a modification of the form of such a difficult-to-adhere base material, a composite composed of a combination of a three-dimensional structure made of a hardly-adhesive base material and metal parts, ceramic parts, glass parts, paper parts, wooden parts, etc. A structure is also preferred.

2. Intermediate layer and decorative member (1) Intermediate layer The intermediate layer is preferably, for example, a primer layer or an adhesion improving layer, or is preferably a foamed layer or a cushion layer.

  This is because the primer layer and the adhesion improving layer can remarkably improve the adhesive strength between the hardly adhesive substrate and the decorative member. Moreover, it is because by providing a foam layer or a cushion layer, it is possible to provide a three-dimensional decorative body that is more excellent in three-dimensional effect and has appropriate cushioning properties.

Moreover, the kind of intermediate | middle layer is although it does not restrict | limit in particular, For example, a urethane resin, an epoxy resin, an acrylic resin, a silane coupling agent, a polyester resin etc. are mentioned.
Although the thickness of the intermediate layer depends on its function, for example, in the case of a primer layer or an adhesion improving layer, the value is preferably in the range of 0.1 to 100 μm, and in the case of a foam layer or a cushion layer Is preferably set to a value in the range of 0.1 to 10 mm.

(2) Decoration member Moreover, it is preferable that the decoration member is comprised from at least 1 resin of an epoxy resin, a vinyl chloride resin, an acrylic resin, an olefin resin, a urethane resin, a polycarbonate resin, or a polyester resin.

The reason for this is that a decorative member having high versatility, low cost, and excellent decorativeness can be used with this configuration. That is, it is possible to provide a three-dimensional decorative body that is inexpensive and excellent in decorativeness.
However, since it is suitable for powder slush molding described later, it is more preferable to use an epoxy resin of B stage (semi-cured state).

  Moreover, it is preferable to make the thickness of a decoration member into the value within the range of 10-500 micrometers. This is because the mechanical strength and durability of the decorative member may be significantly reduced when the thickness of the decorative member is less than 10 μm. On the other hand, if the thickness of the decorative member exceeds 500 μm, it may be difficult to handle or bond. Therefore, it is more preferable to set the thickness of the decorative member to a value within the range of 25 to 300 μm.

  Moreover, the form of the decorative member is preferably a flat film because it is easy to adhere and handle, but since it is more decorative, it has an embossing treatment and an opening (including slits) on the surface. It is also preferable that it is provided. Furthermore, it is preferable that predetermined | prescribed printing and coloring are given to the surface and the inside of the decoration member.

Further, the decorative member is preferably powder slush molded as shown in FIGS. 16 (a) to 16 (c) and FIGS. 17 (a) to 17 (c).
The reason for this is that a decorative member made of powder slush is excellent in three-dimensionality, has a special shape, and has a large dimension (for example, a width of 1 m or more) to a small dimension (for example, a width of 10 cm or less). This is because a decorative member of any size can be provided.

  Note that the powder slush molding process shown in FIGS. 16A to 16C and FIGS. 17A to 17C will be described in detail in the second embodiment, and the description thereof is omitted here.

3. Fuel gas (1) Silane compound (1) -1 boiling point It is preferable to make the boiling point (under atmospheric pressure) of a silane compound into the value within the range of 10-100 degreeC.
This is because, when the boiling point of such a silane compound is less than 10 ° C., the volatility is so strong that it may be difficult to handle. On the other hand, when the boiling point of such a silane compound exceeds 100 ° C., the mixing property with a flammable gas such as air or a combustion aid is remarkably lowered, and the silane compound easily burns incompletely, and the surface of the hardly adhesive substrate This is because the modification may become uneven or it may be difficult to maintain the modification effect for a long time.

Therefore, the boiling point of the silane compound is more preferably set to a value within the range of 15 to 80 ° C, and further preferably set to a value within the range of 20 to 60 ° C.
The boiling point of the silane compound can also be adjusted by restricting the structure of the silane compound itself, but other than that, an alkylsilane compound having a relatively low boiling point, an alkoxylane compound having a relatively high boiling point, etc. Can also be adjusted by appropriately mixing and using.

(1) -2 types The types of silane compounds are not particularly limited, and examples thereof include alkylsilane compounds, alkoxysilane compounds, and modified products thereof.
Of these compounds, alkylsilane compounds are preferred silane compounds because they generally have a low boiling point and can be easily vaporized by heating and uniformly mixed with air or the like.

  Preferred examples of such alkylsilane compounds include tetramethylsilane, tetraethylsilane, 1,2-dichlorotetramethylsilane, 1,2-diphenyltetramethylsilane, 1,2-dichlorotetraethylsilane, 1,2-diphenyl. Examples thereof include tetraethylsilane, 1,2,3-trichlorotetramethylsilane, 1,2,3-triphenyltetramethylsilane, one kind alone or a combination of two or more kinds.

  Furthermore, among such alkylsilane compounds, tetramethylsilane and tetraethylsilane are preferred silane compounds because they have a particularly low boiling point and can be easily mixed with air or the like, and halogens such as 1,2-dichlorotetramethylsilane. A silane compound is a preferred silane compound because of its particularly excellent surface modification effect.

  Of the above-mentioned compounds, alkoxysilane compounds generally have a high boiling point due to their ester structure, but as long as the boiling point is within the range of 10 to 100 ° C. On the other hand, it is a preferred silane compound because it can exhibit a more excellent surface modification effect.

(1) -3 Average molecular weight Moreover, it is preferable to make the average molecular weight of a silane compound into the value within the range of 50-1,000 in a mass-spectrum measurement.

  This is because when the average molecular weight of the silane compound is less than 50, the volatility is high and handling may be difficult. On the other hand, when the average molecular weight of the silane compound exceeds 1,000, it may be difficult to easily vaporize by heating and to be mixed with air or the like.

  Therefore, the average molecular weight of the silane compound is more preferably set to a value within the range of 60 to 500, and more preferably within the range of 70 to 200 in the mass spectrum measurement.

(1) -4 density Moreover, it is preferable to make the density in the liquid state of a silane compound into the value within the range of 0.3-0.9 g / cm < ³ >.

This is because, when the density of the silane compound is less than 0.3 g / cm ³ , handling may be difficult or it may be difficult to accommodate in an aerosol can. On the other hand, when the density of the silane compound exceeds 0.9 g / cm ³ , it is difficult to vaporize, and may be completely separated from air or the like when housed in an aerosol can.

Therefore, it is more preferable to set the density of the silane compound to a value in the range of 0.4 to 0.8 g / cm ^3, still more preferably a value within the range of 0.5~0.7g / cm ³ .

(1) -5 addition amount Moreover, it is preferable to make the addition amount of a silane compound into the value within the range of 1 * 10 < ^-10 > ^-10 mol%, when the whole quantity of combustion gas is 100 mol%.

The reason for this is that when the amount of the silane compound added is less than 1 × 10 ⁻¹⁰ mol%, the modification effect on the hardly adhesive substrate may not be exhibited. On the other hand, when the added amount of the silane compound exceeds 10 mol%, the mixing property between the silane compound and air is lowered, and the silane compound may be burnt incompletely along with it.

Therefore, the addition amount of the silane compound, when the total amount of combustion gas is 100 mol%, and more preferably a value within the range of 1 × 10 ^-9 to 5 mol%, 1 × 10 ^-8 ~ More preferably, the value is within the range of 1 mol%.

(2) Flammable gas In addition, since the flame temperature can be easily controlled, it is usually preferable to add a flammable gas to the combustion gas. Examples of such flammable gases include hydrocarbon gases such as propane gas and natural gas, or flammable gases such as hydrogen, oxygen, and air. In addition, when using combustion gas in an aerosol can, it is preferable to use propane gas, compressed air, etc. as such flammable gas.

  Moreover, it is preferable to make content of such flammable gas into the value within the range of 80-99.9 mol%, when the whole amount of combustion gas is 100 mol%.

  The reason for this is that when the content of the flammable gas is less than 80 mol%, the mixing property between the silane compound and air or the like is lowered, and the silane compound may be incompletely combusted accordingly. On the other hand, when the amount of the silane compound added exceeds 99.9 mol%, the modification effect on the hardly adhesive substrate may not be exhibited.

  Therefore, the addition amount of the silane compound is more preferably a value within the range of 85 to 99 mol%, and a value within the range of 90 to 99 mol%, when the total amount of the combustion gas is 100 mol%. More preferably.

(3) Carrier gas It is also preferable to add a carrier gas in order to uniformly mix the silane compound in the combustion gas. That is, it is preferable that the silane compound and the carrier gas are mixed in advance and then mixed with a flammable gas such as an air flow.

  This is because by adding such a carrier gas, even when a silane compound having a relatively large molecular weight and is difficult to move is used, it can be uniformly mixed with an air stream. That is, by adding the carrier gas, the silane compound can be easily burned, and the surface modification of the hardly-adhesive substrate can be performed uniformly and sufficiently.

  In addition, it is preferable to use the same kind of gas as the flammable gas as such a preferable carrier gas, and examples thereof include hydrocarbons such as air, oxygen, propane gas, and natural gas.

(4) Additive (4) -1 type Further, at least one compound selected from the group consisting of an alkylsilane compound having a boiling point of 100 ° C. or higher, an alkoxysilane compound, and a modified product thereof is modified in the combustion gas. It is preferable to add as a quality aid.

  The reason for this is that even if the compound has a slightly higher boiling point, it is a fuel due to the low boiling point of the silane compound by adding a modification aid that is extremely compatible with silane compounds such as alkylsilane compounds. This is because the poor handling of the gas can be improved, and the surface modification effect on the hardly adhesive substrate can be further enhanced.

(4) -2 addition amount When the total amount of the silane compound is 100 mol%, the addition amount of the modifying auxiliary agent is preferably set to a value within the range of 0.01 to 50 mol%.

  The reason for this is that when the amount of the modification aid added is less than 0.01 mol%, the modification aid addition effect may not be exhibited. On the other hand, if the amount of the reforming auxiliary added exceeds 50 mol%, incomplete combustion of the combustion gas may occur.

  Therefore, when the total amount of the silane compound is 100 mol%, it is more preferable that the amount of the modifying auxiliary added is in the range of 0.1 to 30 mol%, and 0.5 to 20 mol%. It is more preferable to set the value within the range.

[Second Embodiment]
As illustrated in FIG. 9, the second embodiment is a method of manufacturing a three-dimensional decorative body 50 including an intermediate layer 56 and a decorative member 54 on a three-dimensionally processed difficult-to-adhere base material 58. A method for producing a three-dimensional decorative body comprising the following steps (1) and (2).
(1) A step of performing a treatment with a flame 34 derived from a fuel gas containing a silane compound on the surface of the hardly adhesive substrate 58 and / or the surface of the intermediate layer 56 (hereinafter referred to as silicic acid flame) Sometimes referred to as a processing step.)
(2) A process of forming the decorative member 54 above the intermediate layer 56 (hereinafter, sometimes referred to as a decorative process).
That is, in a method for producing a three-dimensional decorative body comprising an intermediate layer and a decorative member formed by powder slush molding on a three-dimensionally processed difficult-to-adhere substrate, the difficult-to-adhere substrate is an olefin resin, It is composed of at least one of a urethane resin, a fluororesin, a silicone resin, and a polyester resin, and on the surface on the intermediate layer side of the hardly adhesive substrate and the surface on the decorative member side of the intermediate layer, or any A step of performing a flame treatment derived from a fuel gas containing a silane compound having a boiling point (under atmospheric pressure) of 10 to 100 ° C. on one of the surfaces, a step of laminating a decorative member above the intermediate layer, It is a manufacturing method of the three-dimensional ornamental body characterized by including this.

1. Silicic acid flame treatment process (1) Fuel gas Since the same silane compound and flammable gas as having demonstrated in 1st Embodiment can be used, description here is abbreviate | omitted.

(2) Flame treatment condition (2) -1 flame temperature It is preferable to make flame temperature in silicic acid flame treatment into the value within the range of 500-1500 degreeC.

  This is because when the flame temperature is less than 500 ° C., it may be difficult to effectively prevent incomplete combustion of the silane compound. On the other hand, when the temperature of the flame exceeds 1500 ° C., the difficult-to-adhere base material to be surface-modified may be thermally deformed or thermally deteriorated. This is because may be excessively limited.

Therefore, the flame temperature is preferably set to a value within the range of 550 to 1200 ° C, and more preferably set to a value within the range of 600 to less than 900 ° C.
The flame temperature is a temperature measured at the tip of the flame, and is appropriately adjusted depending on the type of combustion gas used, the flow rate of the combustion gas, or the type and amount of the silane compound added to the combustion gas. can do.

(2) -2 Processing Time It is preferable to set the flame processing time (injection time) in the silicic acid flame processing to a value within the range of 0.1 seconds to 100 seconds.

  This is because when the flame treatment time is less than 0.1 seconds, the modification effect of the silane compound may not be expressed uniformly. On the other hand, if the flame treatment time exceeds 100 seconds, the difficult-to-adhere base material to be surface-modified may be thermally deformed or thermally deteriorated. This is because the type may be excessively limited.

  Therefore, the flame treatment time is preferably set to a value in the range of 0.3 to 30 seconds, and more preferably set to a value in the range of 0.5 to 20 seconds.

(3) Wetting index (surface energy)
(3) -1 After surface modification Moreover, it is preferable that the wetting index (measurement temperature 25 degreeC) shall be a value within the range of 40-80 dyn / cm in the surface-modified hardly adhesive base material.

  This is because, when the wetting index of the hardly adhesive substrate is less than 45 dyn / cm, it may be difficult to easily perform adhesion, printing, painting, and the like. On the other hand, if the wetting index of the hardly adhesive substrate exceeds 80 dyn / cm, surface treatment is excessively performed, and the hardly adhesive substrate may be thermally deteriorated.

  Therefore, in the surface-modified hard-to-adhere substrate, the wetting index is more preferably set to a value within the range of 45 to 75 dyn / cm, and further preferably set to a value within the range of 50 to 70 dyn / cm. .

(3) -2 Before surface modification In addition, in the hardly adhesive substrate before surface modification (before surface treatment), the wetting index (measurement temperature 25 ° C.) is set to a value in the range of 20 to 45 dyn / cm. Is preferred.

  The reason for this is that when the wetting index of the hardly-adhesive substrate becomes a value less than 20 dyn / cm, surface treatment is performed for a long time, and the hardly-adhesive substrate may be thermally deteriorated. . On the other hand, when the wetting index of the hardly adhesive substrate exceeds 45 dyn / cm, it may be difficult to efficiently perform the surface treatment with a flame. For example, the wetness index of the polyethylene resin before the modification treatment is about 40 dyn / cm, and the wetness index is about 60 dyn by the siliceous flame treatment for about 1 second although it depends on the temperature of the silicic acid flame treatment. / Cm or higher.

  Therefore, it is more preferable to set the wetting index (measurement temperature 25 ° C.) to a value in the range of 25 to 38 dyn / cm in the hardly adhesive substrate before surface modification (before surface treatment), and 28 to 36 dyn / cm. It is more preferable to set the value within the range.

(4) Contact angle (4) -1 after surface modification Moreover, in the surface-modified hard-to-adhere adhesive substrate, the contact angle (measurement temperature 25 ° C.) measured using water is 0.1 to 30 °. It is preferable to set the value within the range.

  The reason for this is that when the contact angle of the hardly-adhesive substrate is less than 0.1 °, surface treatment is excessively performed, and the hardly-adhesive substrate may be thermally deteriorated. . On the other hand, when the contact angle of the hardly adhesive substrate exceeds 30 °, it may be difficult to easily perform adhesion, printing, painting, and the like.

  Therefore, it is more preferable that the contact angle (measurement temperature 25 ° C.) measured using water is set to a value within the range of 0.5 to 20 ° in the surface-modified hard-to-adhere substrate. More preferably, the value is within a range of 10 °.

  Here, Table 1 shows the wetting index (dyn / cm) of the hardly-adhesive substrate before the surface treatment measured using a reference solution at 25 ° C. and the hardly-adhesive group after the surface treatment (0.5 seconds). An example of measuring the wetting index of a material is shown.

(4) -2 Before surface modification Also, in a hardly adhesive substrate before surface modification (before surface treatment), the contact angle (measurement temperature 25 ° C.) measured using water is in the range of 50 to 120 °. It is preferable to set the value within the range.

  This is because, when the contact angle of the hardly adhesive substrate becomes a value of less than 50 °, it may be difficult to efficiently perform the surface treatment by the flame. On the other hand, when the contact angle of such a hardly-adhesive substrate exceeds 120 °, surface treatment is performed for a long time, and the hardly-adhesive substrate may be thermally deteriorated. For example, the contact angle of the polytetrafluoroethylene resin before the modification treatment is about 108 °, which depends on the temperature of the silicic acid flame treatment and the like. Can be reduced to a value of less than about 20 °.

  Therefore, in the hard-to-adhere base material before surface modification (before surface treatment), the contact angle measured using water is more preferably set to a value within the range of 60 to 110 °, and 80 to 100 °. More preferably, the value is within the range.

(5) Surface Modification Device As shown in FIG. 10, a storage tank 12 for storing the silane compound 14, a transfer unit 24 for transferring fuel gas, and an injection unit for blowing a flame 34 of fuel gas It is preferable that the surface modification device 10 for a hard-to-adhere base material including 32.

(5) -1 storage tank As shown in FIG. 10, the 1st storage tank 12 for storing the silane compound 14 which has the heating means 16, and the 2nd for storing flammable gas, such as compressed air And a storage tank (not shown). In this example, a heating means 16 is provided below the first storage tank 12 from a heater, a heat transfer wire, a heating plate connected to a heat exchanger or the like, and a liquid silane compound 14 is added at room temperature and normal pressure. Vaporization is preferred.

  And when surface-treating a difficult-to-adhere substrate, the silane compound 14 in the first storage tank 12 is heated to a predetermined temperature by the heating means 16 and vaporized in a vaporized state (air or the like). It is preferable to mix it with) to make a combustion gas.

  Since the content of the silane compound in the combustion gas is extremely important, a pressure gauge (or liquid level meter) 18 is provided in the first storage tank 12 in order to indirectly control the content of the silane compound. It is preferable to monitor the vapor pressure (or silane compound amount) of the silane compound.

(5) -2 Transfer Unit The transfer unit is usually a pipe structure, and as shown in FIG. 10, the silane compound 14 transferred from the first storage tank 12 and the second storage tank (not shown). The mixing chamber 22 for uniformly mixing the flammable gas (air) transferred from the gas) and making it into a combustion gas is provided, and the valve or flow meter for controlling the flow rate or the pressure of the combustion gas is controlled. It is preferable that a pressure gauge 28 is provided.

  It is also preferable to provide the mixing chamber 22 with a mixing pump, a baffle plate for extending the residence time, etc. so that the flow rate can be strictly controlled after the silane compound and the flammable gas are uniformly mixed.

(5) -3 injection part
As shown in FIG. 10, the injection unit includes a burner 32 for burning the combustion gas sent through the transfer unit 24 and spraying the obtained flame 34 onto the hardly-adhesive substrate that is the object to be processed. It is preferable. The type of the burner is not particularly limited, and may be any of a premix burner, a diffusion burner, a partial premix burner, a spray burner, an evaporation burner, a pulverized coal burner, and the like. Also, the form of the burner is not particularly limited, and for example, as shown in FIG. 10, it may be enlarged toward the tip and may have a fan-shaped configuration as a whole, or as shown in FIG. As described above, it may be a burner having a substantially rectangular shape and the injection ports 64 arranged in the lateral direction.

In addition, it is preferable to determine the arrangement of the injection unit, that is, the arrangement of the burner in consideration of the ease of surface modification of the hardly-adhesive base material that is the object to be processed.
For example, as shown in FIG. 12, it is also preferable to arrange along a circle or an ellipse, or as shown in FIG. preferable.

  Moreover, as shown to Fig.13 (a), it is also preferable to arrange | position to the one side of the hard-to-adhere base material which is a to-be-processed object by predetermined distance, and to-be-processed object is shown in FIG.13 (b). It is also preferable to arrange them at predetermined distances on both sides of the hardly adhesive substrate.

(5) -4 form As shown in FIG. 10, for example, the form of the surface modification device for a hardly-adhesive base material is a storage tank 12, a transfer unit 24 for transferring a fuel gas, and a fuel gas. The injection unit 32 for spraying the flame obtained from the above is installed in a state where it is mounted, while being placed on a fixing jig 38 on the rotary table 36 as shown in FIG. It is preferable to spray the flame 34 from the injection unit 32 while appropriately changing the position of the conductive base material and rotating with the fixing jig 38.

  With such an installation-type surface modification device 10, it is possible to efficiently modify the surface of a difficult-to-adhere substrate that is an object to be processed in a large amount and efficiently.

  Moreover, it is also preferable to make the surface modification apparatus 42 of a hard-to-adhere base material portable as shown in FIG. That is, as shown in a region surrounded by a dotted line, a cartridge-type storage tank 46, a piping pipe 47, and a box 44 having a flow meter and a pressure gauge are prepared, and a burner is provided at the tip of the piping pipe 47. 32 is preferably provided. If comprised in this way, it will become possible to implement surface treatment easily also to the to-be-processed object put on the outdoors, and a large-area to-be-processed object by moving the box 44 suitably. Become.

  In order to facilitate the carrying of the box 44, it is preferable to attach a handle or a single string to the upper part of the box 44 or set the total weight of the box 44 to a value of 20 kg or less.

2. Decoration process (1) Decoration member Since the decoration member used in the decoration process is excellent in three-dimensional effect and form and can be selected in any size, FIGS. 16 (a) to (c) and FIGS. 17 (a) to (a) It is preferable to use a powder slush molded decorative member as exemplified in c).

  Here, FIG. 16A shows a process of heating the metal slash mold 82 having the molding surface 85 by a heating device 86 using, for example, gas or electricity as a heat source. Here, it is preferable to heat the slush mold 82 to a temperature at which the powder resin melts. The shape of the molding surface 85 of the molding die 84 of the slash mold 82 to be used is preferably determined by the shape of the resin molded product to be manufactured.

  FIG. 16B shows a heated slush mold 82 and a reservoir tank 88 containing a flowing powder resin 92 with the molding surface 85 of the molding die 84 facing downward, and the opening surface of the reservoir tank 88. This is a step of integrally connecting the upper and lower sides in a state in which is directed upward.

  FIG. 16C shows a process of forming a resin film 94 having a predetermined thickness on the molding surface 85 of the molding die 84 of the slash die 82 by rotating the slash die 82 and the reservoir tank 88. is there. That is, it is preferable to invert the slash mold 82 and the reservoir tank 88 up and down. This is because the powder resin 92 in the reservoir tank 88 falls on the molding surface 85 of the molding die 84 due to its own weight, and therefore the resin 94 in contact with the molding surface 85 and the resin 94 up to a certain portion to be laminated are separated from the molding die 84. This is because it becomes a molten state by the heat of and adheres to the molding surface 85 as a surface layer.

FIG. 17A shows a process of removing the reservoir tank 88 from the slash mold 82 with the resin film 94 having a predetermined thickness formed on the mold 84.
FIG. 17B shows a process of curing the resin film 94 by cooling the entire slash mold 82 or the mold 84 with a cooling means 98 such as water cooling or air cooling.
FIG. 17C shows a process of peeling the resin film 94 from the mold 84, that is, removing the mold.

(2) Lamination process Moreover, when laminating the decorative member 54 on the hardly adhesive base material 58, it is preferable to form the intermediate | middle layer 56 previously, as illustrated in FIG. For example, it is preferable to provide a primer treatment or an adhesion adjusting layer.

  However, since the process can be further simplified and expedited, as illustrated in FIG. 19, after the material that is the raw material of the intermediate layer 56 is formed on the hardly adhesive substrate 58, the decorative member 54 is further formed thereon. It is preferable to carry out adhesive fixing of the decorative member 54 and formation of the intermediate layer 56 at the same time by heating or irradiating ultraviolet rays in the laminated state.

[Example 1]
1. Production of three-dimensional decorative body A three-dimensionally processed difficult-to-adhere base material was prepared. That is, a vehicle front panel substrate made of polypropylene was prepared.
Next, a silicic acid flame treatment was performed on the surface of the vehicle front panel base material. That is, the treatment with the flame derived from the fuel gas containing the silane compound was performed so that the intermediate layer and the decorative member could be firmly bonded to the base material.

  Next, a foamed urethane agent was applied and formed, and a decorative member was formed. Then, it heated on 30-60 degreeC and the conditions for 1 to 5 minutes, and while making the foaming urethane agent as an intermediate | middle layer foam, a decorative member was adhere | attached and it was set as the vehicle front panel.

2. Evaluation of Difficult-to-Adhere Substrate The wetting index of the vehicle front panel substrate at the stage where the silicic acid flame treatment was performed was measured using a standard solution. Further, the wetting index of the vehicle front panel base material before the silicic acid flame treatment was measured in the same manner.

3. Evaluation of the three-dimensional decorative body The peeling force of the decorative member in the vehicle front panel obtained by forming the urethane foam layer and the decorative member on the vehicle front panel base material is measured by a cross-cut test (JIS standard), Evaluation was made according to the following criteria.
Also,
A: No peeling at 100 cross-cut test.
A: The number of peeling is 1 to 2 in a 100 cross cut test.
(Triangle | delta): The number of peeling is 3-10 pieces in a 100 cross cut test.
X: The number of peeling is 11 or more in a 100 cross section test.

[Examples 2 to 7]
In Examples 2-7, as shown in Table 1, the type of the hardly-adhesive base material constituting the vehicle front panel base material and the silicic acid flame treatment time for the vehicle front panel base material were changed. As in Example 1, the vehicle front panel base material and the three-dimensional decorative body were evaluated.

[Comparative Example 1]
The vehicle front panel base material and the three-dimensional decoration are the same as in Example 1, except that the mixed gas containing the silane compound in Example 1 is replaced with a fuel gas composed of compressed air and propane not containing the silane compound. Each body was evaluated.

  As described above, according to the three-dimensional decorative body and the method for producing the same of the present invention, the surface of the three-dimensionally difficult-to-adhere adhesive substrate and the surface of the intermediate layer, or one of the surfaces includes a silane compound. By applying a flame treatment derived from the fuel gas, it is possible to firmly connect between the three-dimensionally difficult-to-adhesive substrate and the decorative member via the intermediate layer without performing a special primer treatment or the like. Adhesive strength can be obtained.

  In addition, according to the method for producing a three-dimensional decorative body of the present invention, the surface of the three-dimensionally difficult-to-adhesive substrate and the surface of the intermediate layer, or one of the surfaces is derived from a fuel gas containing a silane compound. By applying the flame treatment, a strong adhesive force can be obtained between the three-dimensionally difficult-to-adhere base material and the decorative member via the intermediate layer without performing a special primer treatment or the like. The three-dimensional decorative body can be provided efficiently and quickly.

It is a figure provided in order to demonstrate the three-dimensional ornament which concerns on the 1st Embodiment of this invention. It is a perspective view of an in front panel. It is a perspective view of a door. It is a perspective view of a sheet. It is a perspective view of a console box. It is a perspective view of the interior material with which a door is attached. It is a perspective view of a bumper. It is a perspective view of an ornament. It is a figure provided in order to demonstrate the manufacturing method of the three-dimensional ornament which concerns on this invention. It is a figure provided in order to demonstrate the structure of a surface modification apparatus. It is a figure provided in order to demonstrate how to spray a flame (the 1). It is a figure provided in order to demonstrate how to spray a flame (the 2). It is a figure provided in order to demonstrate how to spray a flame (the 3). It is a figure provided in order to demonstrate the spraying method of the flame of a surface modification apparatus. It is a figure provided in order to demonstrate a portable surface modification apparatus. It is a figure provided in order to demonstrate the method of carrying out the slush powder shaping | molding of a decoration member (the 1). It is a figure with which it uses for demonstrating the method to shape | mold a decorative member to slush powder (the 2). It is a figure provided in order to demonstrate the lamination | stacking method of a decorative member (the 1). It is a figure provided in order to demonstrate the lamination | stacking method of a decorative member (the 2).

Claims (7)

In a three-dimensional decorative body provided with an intermediate layer and a decorative member formed by powder slush molding on a three-dimensionally processed difficult-to-adhere base material,
The hard-to-adhere substrate is composed of at least one of olefin resin, urethane resin, fluororesin, silicone resin, and polyester resin; and
Fuel gas containing a silane compound having a boiling point (under atmospheric pressure) of 10 to 100 ° C. on the surface on the intermediate layer side in the hardly adhesive substrate and the surface on the decorative member side in the intermediate layer, or any one surface A three-dimensional decorative body characterized by being subjected to a flame treatment derived from the above.   The three-dimensional decorative body according to claim 1, wherein the intermediate layer is a foam layer or a cushion layer.   The three-dimensional decoration according to claim 1 or 2, wherein the decorative member is made of at least one of an epoxy resin, a vinyl chloride resin, an acrylic resin, an olefin resin, a urethane resin, and a polyester resin. body.   4. The steric compound according to claim 1, wherein the silane compound is at least one compound selected from the group consisting of an alkylsilane compound, an alkoxysilane compound, and a modified product thereof. Decorative body. The wetness index (measurement temperature 25 ° C.) of the surface of the hardly adhesive substrate and / or the intermediate layer after the flame treatment is set to a value within the range of 40 to 80 dyn / cm. The three-dimensional decorative body according to any one of claims 1 to 4, wherein:   The three-dimensional decoration according to any one of claims 1 to 5, comprising at least one vehicle part selected from the group consisting of an in-front panel, a door, a chair, a console box, an interior material, a bumper, and an ornament. body. In the method for producing a three-dimensional decorative body comprising a three-dimensionally processed difficult-to-adhere base material, an intermediate layer, and a decorative member formed by powder slush molding ,
The hard-to-adhere substrate is composed of at least one of olefin resin, urethane resin, fluororesin, silicone resin, and polyester resin; and
Fuel gas containing a silane compound having a boiling point (under atmospheric pressure) of 10 to 100 ° C. on the surface on the intermediate layer side in the hardly adhesive substrate and the surface on the decorative member side in the intermediate layer , or any one surface Carrying out the flame treatment derived from,
A step of laminating the decorative member above the intermediate layer ;
The manufacturing method of the three-dimensional ornamental body characterized by including.