JPH0812911A - X-ray-absorbing coating agent and platy material produced using same - Google Patents

Abstract

PURPOSE:To obtain a coating agent which is applied to an object having a low X-ray absorption capability and being difficult of nondestructive inspection and which enables an effective nondestructive inspection of it by compounding a metal component having specified properties with a binder component. CONSTITUTION:This coating agent is produced by compounding a metal component satisfying the relation: Z.rho>=300 (wherein Z is the atomic number and rhois the density [g.cm<-2>] of a metal constituting the component) and a binder component. Examples of the metal component are Ag, Sn, La, Pt and W. Pref. examples of the binder component are a polyester acrylate, cellulose acetate, and a styrene-butadiene block copolymer. The agent is dissolved in a solvent and applied to a substrate 2 (e.g. an aluminum plate) to form an X-ray-absorbing layer 3, thus giving a platy material 1. The material 1 is incorporated into a resin molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an X-ray absorbing coating agent and a plate material using the same, and more specifically to X-ray absorbing coating agent.
An X-ray absorbing coating agent which enables effective non-destructive inspection by applying it to an object having low X-ray absorbing ability and difficult to non-destructive inspection, and an X-ray absorbing layer formed by applying the X-ray absorbing coating agent. And a plate material having

[0002]

2. Description of the Related Art Non-destructive inspection using X-rays has come to be carried out in various fields because it is possible to know the state of the inside of a test object without damaging the test object.

On the other hand, as the applications of resin molded products have expanded, resin molded products incorporating constituent members such as heaters have also been put into practical use. Then, such a resin molded product is manufactured, for example, by further injecting resin into a resin molded body in which constituent members such as a heater are housed and placed at a predetermined position.

[0004]

However, the nondestructive inspection using X-rays is performed by displaying the difference in the X-ray absorptivity of the test object as the difference in image contrast and visually recognizing this image. Therefore, if the X-ray absorptivity of the test object is low, a difference in contrast may not appear in the image, and such a test object can be effectively subjected to nondestructive inspection using X-rays. There is a problem that you cannot do it.

Further, in the case where a resin molded body containing a plate material which is a constituent member such as a heater is manufactured as described above, a functional plate such as a heat transfer plate is generally formed of a thin base material. The functional plate, which should be a flat plate, may be bent or damaged by the resin pressure during injection molding. Further, if the resin molded product is opaque, it may not be possible to confirm whether or not the plate material is embedded.

Therefore, it is necessary to perform a non-destructive inspection on a resin molded body containing a plate material in a state of a completed product in which the plate material is embedded. However,
For the resin that forms the resin molding containing the plate material,
In general, a flame retardant component using a metal such as antimony (Sb) as a flame retardant aid is added, and such a flame retardant component has a relatively high X-ray absorption ability, and therefore functions such as a heat transfer plate. If the plate is a metal having a low X-ray absorption ability, as typified by an aluminum plate, the state of the functional plate cannot be visually recognized as an image with clear contrast, and nondestructive inspection cannot be effectively performed. is there.

The present invention has been made in view of the above circumstances, and an object of the present invention is to apply a non-destructive inspection utilizing X-rays by applying it to an object having a low X-ray absorption ability. X-ray absorptivity that makes it possible to perform non-destructive inspection effectively even on an object that cannot be subjected to non-destructive inspection using X-rays It is intended to provide a coating material and a plate material having an X-ray absorption layer using the coating material.

[0008]

In order to solve the above-mentioned problems, the X-ray absorbing coating agent of the present invention is an X-ray absorbing coating agent containing a metal component and a binder component. Has a structure in which Z · ρ ≧ 300 when the atomic number of the constituent metal of the metal component is Z and the density is ρ [g · cm ⁻² ].

The plate material of the present invention is a member to be incorporated in a molded body of resin and has an X-ray absorbing layer formed by applying the above X-ray absorbing coating agent on a substrate. did.

[0010]

The X-ray absorbing coating agent of the present invention contains a metal component and a binder component, and the metal component has the atomic number Z of the constituent metal of the metal component and the density ρ [g · cm ⁻² ]
Then, Z · ρ ≧ 300 is satisfied.

Here, regarding the X-ray absorption characteristics of metals, when the X-ray quality is the same, the absorption coefficient increases as the weight of the metal increases, and as the atomic number increases, the X-ray transmittance decreases. That is, the absorption coefficient μ of the substance for X-rays of wavelength λ
Is the following formula: μ = C · λ ³ · Z · ρ [cm ³ ] (where C is a constant, λ is the wavelength, Z is the atomic number, and ρ is the density of the substance. Therefore, the X-ray absorbing coating agent of the present invention containing a metal whose Z · ρ value satisfies Z · ρ ≧ 300 is applied to an object having a low X-ray absorbing ability. By doing so, it becomes possible to capture such an object as an image with clear contrast in a nondestructive inspection using X-rays, and an effective nondestructive inspection becomes possible.

The plate material of the present invention contains a metal component and a binder component, and the metal component has an atomic number Z of a constituent metal of the metal component and a density ρ [g · c].
m ⁻² ], an X-ray absorbing layer formed by applying an X-ray absorbing coating agent satisfying Z · ρ ≧ 300 is provided on the base material. Therefore, in this plate material, X
Since X-rays are absorbed by the ray absorbing layer, even when this plate material is incorporated in a resin molded body containing a flame retardant aid such as antimony (Sb), non-destructive use of X-rays is possible. By inspection, it is possible to easily know whether or not the base material is embedded and the state of the base material.

[0013]

Next, an embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, the plate material 1 of the present embodiment contains a metal component and a binder component on a base material 2 made of a metal plate, and the metal component is an atomic number of a constituent metal of the metal component. Is Z and the density is ρ [g · cm ⁻² ], the X-ray absorbing layer 3 is formed by applying an X-ray absorbing coating agent satisfying Z · ρ ≧ 300.

The metal forming the metal plate used for the base material 2 can be appropriately selected according to the application of the plate material 1. For example, when the plate material 1 is used as a heat transfer plate of a heater member incorporated in a resin injection molded body, aluminum (Al), copper (Cu), stainless steel (SUS), etc. are preferable.

Although a metal plate is used as the base material 2 in this embodiment, the base material 2 is not limited to a metal plate, and for example, a plastic plate, a paper base material, or a composite product of these is used. You can also

Further, the thickness of the base material 2 can be appropriately determined depending on the use of the plate material 1, the forming material, and the like. For example, when the application of the plate material 1 is a heat transfer plate of a heater member to be incorporated in a resin injection-molded body and the material for forming the base material 2 is aluminum (Al), the thickness of such base material 2 is Is usually about 30 to 120 μm, preferably about 50 to 60 μm.

One or both sides of the base material 2 contains a metal component and a binder component, and the metal constituting the metal component has an atomic number Z and a density ρ [g · cm ⁻² ]. At this time, an X-ray absorbing coating agent satisfying Z · ρ ≧ 300 is applied to form the X-ray absorbing layer 3.

Here, as the above-mentioned metal having a Z · ρ value of 300 or more, for example, Ag (Z · ρ value: 493.0
3), Sn (Z · ρ value: 364.9), La (Z · ρ
Value: 351.69), Pt (Z · ρ value: 1,673.
1), W (Z · ρ value: 1,428.2), Ir (Z · ρ
Value: 1,732.5), Au (Z · ρ value: 1,526.
28) and the like.

The metal component is preferably used in a materially stable oxide state so that the curing rate of the binder component does not become too fast. The binder component is used as a vehicle by being divided into uses such as an overcoat agent, an adhesive, and a pressure-sensitive adhesive.

Specific examples include a resin binder component, an elastomer binder component, a natural binder component and the like. Among the above resin binder components, examples of thermosetting binder components include urea-based, melamine-based, resorcinol-based, phenol-based (water-soluble, alcohol-soluble, novolac), epoxy-based, polyurethane-based, polyaromatic-based ( Polyimide, polybenzimidazole, polyamideimide, etc.), polyester type (alkyd type, unsaturated polyester, diallyl phthalate type, polyester acrylate, acrylic acid diester, etc.) and the like. Examples of thermoplastics include vinyl acetate-based (emulsion, solution), polyvinyl alcohol-based, polyvinyl acetal-based (butyral, acetal, formal, etc.), vinyl chloride-based,
Acrylic type (emulsion, solution, reactive type), polyolefin type (PE, EVA, etc.), cellulose type (cellulose, nitrocellulose, cellulose acetate, ethyl cellulose, water-soluble cellulose, etc.), silicone type, polyacrylamide type, polyvinyl methyl ether type , Polyisobutylene-based, polyvinyl ether and the like.

As the elastomeric binder component,
For example, chloroprene rubber type (solution, latex), nitrile rubber type (solution, latex), SBR type, styrene-ethylene-butylene block copolymer (SEBS)
System, styrene-isoprene block copolymer (SIS)
System, styrene-butadiene block copolymer (SBS)
System, polysulfide system, butyl rubber system, silicone rubber system (RTV type, vulcanization type, pressure sensitive type), isobutylene rubber system, isoprene rubber system, butyl rubber system and the like.

Examples of the mixed system include phenolic vinyl type, epoxy phenol type, phenol chloroprene type, phenol nitrile type, epoxy polyamide type, epoxy polysulfide type, nitrile epoxy type and epoxy type. Examples include nylon.

Examples of natural binder components include natural rubber-based binder components. Here, when the base material 2 is a metal plate, as an overcoating agent for such a base material 2, an acrylic polyol-based one is particularly preferable, and it is used alone or mixed with vinyl chloride, cellulose or the like. It At this time, isocyanate (NCO) is used as a curing agent. In addition, the acrylic polyol preferably has a low OH value in terms of adhesion to metal,
Specifically, those having an OH value of 10 to 30 are preferably used. The X-ray absorptive coating agent containing such an acrylic polyol-based binder component has a function or a function as a reinforcing agent for the base material 2 made of a metal plate together with the X-ray absorbing ability.

Examples of the solvent for such an X-ray absorbing coating agent include toluene and methyl ethyl ketone (ME
K), ethyl acetate, butyl acetate, xylene, methyl isobutyl ketone (MIBK), isopropyl alcohol (IPA) and the like.

For example, the mixing ratio of each component in the X-ray absorbing coating agent using these solvents is usually 20 to 70 parts by weight for the metal component and 10 for the binder component.
-30 parts by weight, and the solvent is usually 20-60 parts by weight.

The ratio (P / V ratio) between the pigment (P) and the vehicle (V) in this X-ray absorbing coating agent.
Is usually 40 to 90, preferably 70 to 80.
When the P / V ratio is as high as 60 or more, various precipitation inhibitors may be used.

X formed by applying this X-ray absorbing coating agent
The dry thickness of the linear absorption layer 3 is usually about 10 to 60 μm, preferably about 30 to 50 μm. An overcoat layer made of, for example, an acrylic resin may be further provided on the X-ray absorbing layer 3, if necessary.

When the X-ray absorbing layer 3 is provided on one side of the metal plate 2, an adhesive layer may be provided on the opposite surface of the metal plate 2. The pressure-sensitive adhesive layer is usually covered with release paper.

FIG. 2 is a conceptual diagram showing an example of the structure when this plate material is used as a heat transfer plate of a heater incorporated in a resin molded body, for example. As shown in FIG. 2, in this resin molded body, a plate material 1 formed by coating an X-ray absorbing coating agent on a metal plate using, for example, an Al foil is built in a molded body 4, and the plate is further provided. Electric wire 5 for heater for material 1
Is attached, and the heater electric wire 5 is connected to a power source 7 via a thermistor 6.

Then, such a resin molded body is manufactured by injection molding as follows, for example. That is,
First, a first mold as shown in FIG. 3 is prepared. As shown in FIG. 3, this first mold is an upper mold 1 having a convex portion 11.
2 and a lower mold 14 having a concave portion 13, and a cavity 20 is formed by clamping both molds.

Next, the cavity 20 is filled with injection resin from the injection gate 15. The molten resin passes through the injection gate 15 and fills the entire cavity 20.

In this way, in the molded body obtained by the injection molding using the first mold, the concave portion 16 corresponding to the convex portion 11 of the upper mold 12 is formed. After that, the heater electric wire 5 is mounted in the concave portion 16 of the molded body.

Next, the molded body in which the heater wire 5 is mounted in the recess 16 is housed in, for example, the lower mold 17 constituting the second mold shown in FIG. In FIG. 4, 18 is an upper mold, and the lower mold 17 and the upper mold 18 form a cavity 21.

The molded product is obtained by sucking air from the suction port 30 provided in the lower mold 17 to obtain the lower mold 17.
It is held in close contact with and fixed to. The heater wire 5 has a plate member 1 used as a heat transfer plate of the heater.
The metal plate 2 of 1 is fixed via the adhesive 40.

Next, the lower die 17 is advanced to move the upper die 1
The lower mold 17 is closed by 8 and the cavity 2
After forming 1, the molten resin is injected from the injection gate 15 'to fill the entire cavity 21 with the resin. As a result, a resin molded body having a heater built therein is obtained.

When the resin molded body thus obtained was subjected to a nondestructive inspection using X-rays, the plate material 1
The X-ray absorbing layer 3 formed in the above absorbs X-rays, and the state of the metal plate 2 used as the heat transfer plate of the heater can be visually recognized as an image with clear contrast.

Further, the resin molded product is not limited to this embodiment as long as the shield material, the coil product, the capacitor, etc. are buried in addition to the heater. Specific examples include a stainless foil shield material, a coil product in which a copper pattern is used as a print coil in a copper / PET film, and a capacitor paper containing kraft pulp as a paper base material. For the nondestructive inspection of the resin molded article, the same as the heater member can be dealt with by applying the X-ray absorbing coating agent of the present invention to the substrate.

Further, the resin molded product is not limited to the injection molded product, but may be an ultrasonically sealed product of two upper and lower molds, a hot press product, or the like. Next, an experimental example of the present invention will be shown to more specifically describe the present invention. Experimental Example 1 Preparation of X-ray absorbing coating agent Acrylic polyol (heating residue 50%, OH value 16) 2
To 0 parts by weight of toluene and methyl ethyl ketone (ME
K), 20 parts by weight each, rotation speed 1,200
While stirring with a mixer of rpm, 80 parts by weight of tungsten trioxide (Z · ρ value of W: 1,428.8) was added little by little and sufficiently dispersed, and X-ray absorbing coating agent sample liquid 1
40 parts by weight were obtained.

Next, an isocyanate curing agent [XEL curing agent (D) manufactured by The Inktech Co., Ltd.] was used for the above sample liquid and the isocyanate curing agent, and the ratio of the acrylic polyol and the isocyanate curing agent in the sample liquid was (Acrylic polyol) / (isocyanate curing agent) = 100/20 were mixed and stirred to obtain an X-ray absorbing coating agent coating liquid. Preparation of plate material The above coating solution was applied to 3 reverse coats to a thickness of 60μ.
m soft aluminum foil, 40 ℃, 4
Cured under the condition of 8 hours, coating thickness 15μ
Three kinds of plate material samples of m, 30 μm and 45 μm were prepared. Nondestructive inspection test Each plate material sample above is laminated with a flame-retardant ABS resin (NC118 made by Japan Synthetic Rubber) molded product (thickness 1.2 mm) and subjected to an X-ray non-destructive inspection tester, and the X-ray absorption capacity is ABS. The difference in contrast with the resin was examined, and the X-ray absorption ability was evaluated in the following four stages. The results are shown in Table 1.

A: The difference in contrast with the ABS resin containing the flame retardant is large and easily identifiable. B: The difference in contrast with the ABS resin containing the flame retardant is identifiable C: Contrast with the ABS resin containing the flame retardant. The difference is small and the identification is difficult. D: There is almost no difference in the contrast with the ABS resin containing the flame retardant, and the identification is extremely difficult. The test conditions of the nondestructive inspection test are as follows.

Usage tester: EV-manufactured by Unihight Co., Ltd.
120 Tube voltage: 25kv Tube current: 2mA

[0042]

[Table 1] Experimental Example 2 In the above Experimental Example 1, lanthanum oxide (Z · ρ value of La: 351.
69) An X-ray absorptive coating agent coating solution was prepared in the same manner as in Experimental Example 1 except that 80 parts by weight was used.
A plate material sample was prepared and a nondestructive inspection test was conducted in the same manner as in Experimental Example 1. The results are shown in Table 1. Comparative Example 1 In the above-mentioned Experimental Example 1, 80 parts by weight of tungsten trioxide was replaced with barium sulfate (Z · ρ value of Ba: 202.
72) An X-ray absorptive coating agent coating solution was prepared in the same manner as in Experimental Example 1 except that 80 parts by weight was used.
A plate material sample was prepared and a nondestructive inspection test was conducted in the same manner as in Experimental Example 1. The results are shown in Table 1. Experimental Example 3 Preparation of X-ray absorbing coating agent Acrylic polyol (heating residue 50%, OH value 16) 5
To 0 parts by weight of toluene and methyl ethyl ketone (ME
K), 50 parts by weight each, and 1,000 rpm
While stirring with a mixer of rpm, 50 parts by weight of tungsten trioxide (Z · ρ value of W: 1,428.8) was added little by little and sufficiently dispersed, and X-ray absorbing coating agent sample liquid 2
00 parts by weight were obtained.

Next, an isocyanate curing agent [XEL curing agent (D) manufactured by The Inktech Co., Ltd.] was used for the sample liquid and the isocyanate curing agent, and the ratio of the acrylic polyol and the isocyanate curing agent in the sample liquid was (Acrylic polyol) / (isocyanate curing agent) = 100/20 were mixed and stirred to obtain an X-ray absorbing coating agent coating liquid. Preparation of plate material The above coating solution was applied to 3 reverse coats to a thickness of 60μ.
m soft aluminum foil, 40 ℃, 4
Cured under the condition of 8 hours, coating thickness 10μ
Three types of plate material samples of m, 25 μm, and 40 μm were prepared. Nondestructive inspection test In the same manner as in Experimental Example 1, the X-ray absorption capacity of each plate material sample was evaluated. The results are shown in Table 1. Experimental Example 4 In the above Experimental Example 3, lanthanum oxide (Z · ρ value of La: 351.
69) An X-ray absorptive coating agent coating solution was prepared in the same manner as in Experimental Example 3 except that 50 parts by weight was used.
A plate material sample was prepared and a nondestructive inspection test was performed in the same manner as in Experimental Example 3. The results are shown in Table 1. Comparative Example 2 In the above-mentioned Experimental Example 3, barium sulfate (Z · ρ value of Ba: 202.
72) An X-ray absorptive coating agent coating solution was prepared in the same manner as in Experimental Example 3 except that 50 parts by weight was used.
A plate material sample was prepared and a nondestructive inspection test was performed in the same manner as in Experimental Example 3. The results are shown in Table 1. Experimental Example 5 A coating solution similar to that obtained in Experimental Example 1 was applied to one surface of a soft Al foil having a thickness of 60 μm to a thickness of 30 μm to form an X-ray absorbing layer while Al was applied. On the other side of the foil, an acrylic adhesive [SK DYN B-5 manufactured by Soken Chemical Industry Co., Ltd.
00S "] was applied by comma coating to a pressure-sensitive adhesive layer having a thickness of 30 µm, and the pressure-sensitive adhesive layer was further covered with release paper having a thickness of 110 µm to prepare a plate material having the following configuration.

X-ray absorbing layer (thickness 30 μm) / soft Al
Foil (thickness 60 μm) / adhesive layer (thickness 30 μm) / release paper (thickness 110 μm) This plate material is used as a heat transfer plate constituting a heater of a resin molded body having a built-in heater as follows. Then, a resin molded body containing a heater was prepared.

That is, first, the release paper of the plate material was peeled and removed, and the plate material was fixed to the heater electric wire installed in the recess of the resin molding having the recess via the adhesive layer.
Next, this resin molded body was housed in the lower mold.

Thereafter, the lower mold is moved to close the upper mold to form a cavity, and molten ABS resin containing a flame retardant is injected from the gate into the cavity to separate the heater wire and the plate material. A resin molded body having a built-in heater was embedded while being embedded.

An X-ray non-destructive inspection was conducted on the resin molded product containing the heater by using the same X-ray non-destructive inspection tester as used in Experimental Example 1 above. The state of the embedded soft Al foil could be observed as an image with clear contrast. Comparative Example 3 In the Experimental Example 5, instead of the same coating solution as that obtained in the Experimental Example 1, an acrylic polyol coating solution containing acrylic polyol, toluene and methyl ethyl ketone (MEK) was used as a soft Al foil. A resin molded body containing a heater was prepared in the same manner as in Experimental Example 5 except that the resin coating was applied to form an overcoat layer, and the resin molded body was subjected to X-ray nondestructive inspection.

As a result, the state of the soft Al foil embedded in the resin molding could not be captured as an image with clear contrast, and the state of the soft Al foil could not be observed.

[0049]

As described in detail above, since the X-ray absorbing coating agent of the present invention is configured to contain a metal component having a certain or more X-ray absorbing ability, this coating agent is applied. Only by doing so, it becomes possible to perform effective X-ray non-destructive inspection even on a test object having a low X-ray absorption ability, which could not be effectively subjected to non-destructive inspection by X-ray.

Further, since the plate material of the present invention has the X-ray absorbing layer formed by coating the above-mentioned X-ray absorbing coating agent on the base material, the X-ray is embedded in the resin molding. When the nondestructive inspection is performed, the state of the base material can be captured as an image with clear contrast, and the state of the base material can be easily observed.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a plate material of the present invention.

FIG. 2 is a conceptual diagram showing a configuration example when a plate material of the present invention is used as a heat transfer plate of a heater incorporated in a resin molded body.

FIG. 3 is an explanatory view showing an example of a first mold used for molding the resin molded body shown in FIG.

FIG. 4 is an explanatory view showing an example of a second mold used for molding the resin molded body shown in FIG.

[Explanation of symbols]

 1 ... Plate material 2 ... Base material 3 ... X-ray absorption layer

Claims (2)

[Claims] 1. An X-ray absorbing coating agent containing a metal component and a binder component, wherein the metal component has an atomic number Z of a constituent metal of the metal component and a density ρ [g · cm ⁻² ].
The X-ray absorbing coating agent is characterized in that Z · ρ ≧ 300. 2. A plate which is a member to be incorporated in a resin molded body and has an X-ray absorbing layer formed by applying the X-ray absorbing coating agent according to claim 1 onto a substrate. Material.