JP2002311019A - Resin laminate inspecting method, and manufacturing method including the inspecting method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the product inspection of a resin laminate consisting of two kinds of different resin, to elucidate causes for defects found therein, and to determine the long-term reliability of the resin laminate. SOLUTION: By exposing the resin laminate comprising a resin layer (A) consisting of a resin (a) and a resin layer (B) consisting of a resin (b) of different kind from the resin (a) to the solvent capable of selectively dissolving the resin (a), and the resin layer (B) left behind is analyzed, or the obtained solution is analyzed. When manufacturing the resin laminate, a part of the manufactured resin laminate is sampled during its manufacturing step, and a step of carrying out an inspection step of the product is performed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for inspecting a resin laminate, and a method for manufacturing a resin laminate including such an inspection step.

[0002]

2. Description of the Related Art Generally, resin laminates are required to have excellent adhesive strength between resin layers. The analysis of the adhesive strength between the resin layers and thus the bonding state is important for product inspection and elucidation of the cause of the accompanying defect, and the result is fed back to optimization of the manufacturing process.

[0003] For product inspection of a resin laminate, conventionally,
Peel strength measurements have been used. However, this measurement did not make it possible to clarify the cause of the failure or the adhesion mechanism.
In order to elucidate the cause of the failure and the adhesion mechanism, a method of analyzing the peeled interface by an analytical means such as ATR-IR and ESCA has been adopted. However, the method of analyzing the peeling interface is that the peeling causes one or both of the two layers forming the bonding interface to undergo deformation such as elongation, and further involves partial material destruction. Was impossible at all.

Further, since it is required that the adhesive strength of the resin laminate does not change for a long time even when the resin laminate is exposed to an environment, it is necessary to determine the long-term reliability in product inspection. Required. However,
It has not been possible to determine long-term reliability by conventional peel strength measurement or peel interface analysis.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and enables a product inspection of a resin laminate composed of two kinds of resins different from each other and an accurate elucidation of a cause of a defect accompanying the product inspection. Can be optimized,
It is another object of the present invention to provide a method for inspecting a resin laminate, which can determine the long-term reliability of the resin laminate, and a method for manufacturing a resin laminate including the same.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, instead of performing a peeling operation on a resin laminate, selectively removing only one resin. It has been found that by dissolving and removing one of the resin layers using a dissolving solvent, it is possible to inspect the product of the resin laminate, elucidate the cause of the accompanying defect, and determine the long-term reliability of the resin laminate. That is, by analyzing the resin layer left by the dissolution and removal of one resin layer by various analysis means, it is possible to accurately know the adhesion state between the resin layers in the resin laminate, and By analyzing the resin solution obtained by dissolution, it has been found that the state of deterioration of the resin laminate can be known.

That is, the present invention provides a resin laminate having a resin layer (A) made of a resin (a) and a resin layer (B) made of a resin (b) different from the resin (a).
Inspection of the resin laminate by exposing the resin (a) to a solvent capable of selectively dissolving the resin (a) and then selectively dissolving and removing the resin (a) and then analyzing the remaining resin layer (B). Is the way.

Further, the present invention provides a resin laminate having a resin layer (A) composed of a resin (a) and a resin layer (B) composed of a resin (b) of a type different from the resin (a). The resin (a) is selectively dissolved by exposing the resin (a) to a solvent capable of selectively dissolving the resin (a).
After obtaining the above solution, the method is also an inspection method of a resin laminate in which the solution is analyzed.

Further, the present invention provides a resin laminate having a resin layer (A) made of a resin (a) and a resin layer (B) made of a resin (b) of a type different from the resin (a). The method is also a method of manufacturing a resin laminate including a step of extracting a part of the manufactured resin laminate during the manufacturing process and performing the inspection method. Hereinafter, the present invention will be described in detail.

The resin laminate in the present invention is not particularly limited, and is a resin laminate having a plurality of resin layers,
Among them, there is no particular limitation as long as it has two layers made of different kinds of resins. However, particularly preferred ones are composed of a polyamide resin layer and a fluororesin layer. This is because the resin laminate composed of polyamide resin and fluororesin has excellent mechanical properties and processability, which are the characteristics of polyamide resin, and excellent chemical resistance and barrier properties to various chemical solutions, which are the characteristics of fluororesin. It has antifouling properties and the like, and takes into account the fact that it is already widely used as a fuel tube for automobiles, a tube for transporting chemicals, and the like. In particular, if the resin soluble in the solvent is the resin (a) and the resin insoluble in the solvent is the resin (b), the resin (a) is a polyamide resin and the resin (b) is a fluororesin. Is preferred.

As an embodiment of the resin laminate in the present invention, first, a two-layer laminate of a resin layer (A) and a resin layer (B) directly laminated (without using an adhesive or the like) on the resin layer (A) is exemplified. Further, a three-layer laminate having an adhesive layer between the resin layer (A) and the resin layer (B) is also possible. In the case where the three-layer laminate is used in the present invention, when the adhesive layer is dissolved in a solvent as in the case of the resin layer (A), the adhesive layer is considered to be included in the resin layer (A). When the layer does not dissolve in the solvent similarly to the resin layer (B), the adhesive layer is considered to be included in the resin layer (B).

In still another embodiment, the above two layers or three layers
Outside the layer (A) and / or the layer (B) of the layer laminate,
Further, those having a layer (C) are exemplified. For this layer (C), any of a thermoplastic resin and an inorganic substance can be used. Further, when the layer (C) is a thermoplastic resin, it may have conductivity. As a method for imparting conductivity to the layer (C), the thermoplastic resin constituting the layer (C) may be used. , By mixing a conductive material.

Examples of the conductive material include metal powders such as copper, nickel, and silver; metal fibers such as iron and stainless steel; carbon-based substances such as carbon black, acetylene black, carbon fiber, and carbon fluoride; carbon black, zinc oxide, and the like. , Glass beads, titanium oxide and the like are preferably coated with metallized inorganic compounds by metal sputtering, electroless plating or the like.

The resin laminate of the present invention includes, for example, tubes and hoses: tubes or hoses for automobile fuel piping, radiator hoses for automobiles, brake hoses,
Air conditioner hoses, electric wire covering materials, optical fiber covering materials, etc. Films and sheets: sliding members requiring high chemical resistance, such as diaphragms of diaphragm pumps and various packings, agricultural films, linings, weather-resistant covers, construction Tanks, such as laminated steel plates used in the home and home appliance fields, etc .: Automotive radiator tanks, chemical liquid bottles,
Chemical liquid tanks, bags, chemical containers, gasoline tanks, etc. Others: Seals for various automobiles such as flange gaskets for carburetors, O-rings for fuel pumps, chemical seals such as seals for chemicals pumps and flow meters, and seals for hydraulic equipment In addition to various mechanical seals and the like, bellows, spacers, rollers, and multilayer molded products such as electronic and electric parts may be used.

[0015] The polyamide resin in the present invention refers to a polymer having an amide bond -NHCO- as a repeating unit in the molecule. Examples of such a resin include a resin in which a majority of amide bonds are bonded to an aliphatic or alicyclic structure, a so-called nylon resin. Specifically, for example, nylon 6, nylon 66,
Nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 46 and polymers of metaxylylenediamine / adipic acid, and blends thereof.

In the polyamide resin of the present invention, a structure having no amide bond as a repeating unit may be partially blocked or graft-bonded. Examples of such a resin include polyamide resin elastomers such as nylon 6 / polyester copolymer, nylon 6 / polyether copolymer, nylon 12 / polyester copolymer, nylon 12 / polyether copolymer, and the like. be able to. These polyamide resin elastomers are block copolymers of a nylon resin oligomer and a polyester resin oligomer or a polyether resin oligomer via an ester bond or an ether bond. Examples of the polyester resin oligomer include polycaprolactone,
Examples of the polyethylene ether adipate and the polyether resin oligomer include, for example, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In a particularly preferred embodiment,
Nylon 6 / polytetramethylene glycol copolymer,
Nylon 12 / polytetramethylene glycol copolymer and the like.

On the other hand, the fluororesin in the present invention may be a resin called “resin” in a narrow sense or a “rubber”.
And what is called an "elastomer", and basically any of various conventionally known ones can be applied. Physical properties such as melting property and melting point of fluororesin,
The presence or absence of the functional group depends on the method of forming the laminate and the like, and is not specified in the present invention.

As a specific example of the fluororesin, it is not suitable for melt molding, but polytetrafluoroethylene (PTFE), which has the highest chemical resistance and solvent resistance among fluororesins, is excellent in melt moldability, and is widely used for laminates. Ethylene-tetrafluoroethylene copolymer (ETFE) used for molding,
Polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoro Ethylene-perfluorovinyl ether copolymer (P
FA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and blends and modified products thereof, and those obtained by introducing an adhesive functional group into a fluororesin.

In the present invention, the resin layer (A) and the resin layer (B) in the resin laminate are formed of various organic or inorganic reinforcements suitable for the respective layers as long as the adhesiveness and other properties of each resin are not impaired. Materials, fillers, plasticizers, stabilizers, heat-resistant agents, ultraviolet absorbers, may have additives such as pigments, especially to prevent electrification, copper, nickel, which imparts conductivity,
Metal powders such as silver; metal fibers such as iron and stainless steel; carbon-based materials such as carbon black, acetylene black, carbon fiber, and carbon fluoride; metal sputtering on surfaces such as carbon black, zinc oxide, glass beads, and titanium oxide And a metallized inorganic compound coated by electroless plating or the like.

First, the inspection method of the present invention will be described. In the analysis of the resin laminate, a resin laminate having a resin layer (A) composed of the resin (a) and a resin layer (B) composed of a resin (b) of a different type from the resin (a) is formed by the resin By exposing (a) to a solvent capable of selectively dissolving, the resin (a) is selectively dissolved and removed, and then the remaining resin layer (B) is analyzed and / or dissolved. By analyzing the solution of the resin (a) obtained by the above. The analysis of the remaining resin layer (B) and the analysis of the solution of the resin (a) obtained by dissolution can be used in combination. In this case, it is preferable because more detailed knowledge can be obtained with respect to the product inspection of the resin laminate and the accompanying cause of the defect and the long-term reliability of the resin laminate.

In the analysis of the resin laminate, first, the resin laminate is exposed to a solvent capable of selectively dissolving the resin (a), and the resin (a) is dissolved and removed. The solvent capable of selectively dissolving the resin (a) is not particularly limited, and can be appropriately determined depending on the combination of the resins used, dissolution conditions, and the like. In the present invention, "capable of selectively dissolving the resin (a)" means that the resin (a) is at least 1 g, preferably at least 3 g, more preferably at least 100 ml of the solvent under the adopted dissolution conditions. It means that 5 g or more is dissolved and the resin (b) is substantially insoluble in the solvent under the above conditions.

In particular, when the resin (a) is a polyamide resin and the resin (b) is a fluororesin, the solvent may be 1,1,1,3,3,3-hexafluoro-2-
Propanol (hereinafter referred to as HFIP), 2,2,2-
Fluorinated alcohols such as trifluoroethanol; m-
Non-fluorine or fluorinated phenol such as cresol, chlorophenol and pentafluorophenol; non-fluorinated such as trifluoroacetic acid and formic acid or fluorinated carboxylic acid, particularly those having high acidity; sulfuric acid And inorganic strong acids. this house,
In particular, a fluorinated alcohol such as HFIP dissolves the polyamide resin very quickly even at room temperature, and does not cause hydrolysis of the polyamide resin.

The exposure of the resin laminate to the solvent is carried out by placing the resin laminate as a sample in the solvent and physically stirring it with a shaker, mill or the like. The solvent is replaced several times as necessary to completely dissolve and remove the resin layer (A), and then the sample is pulled up from the solvent and dried. The drying is preferably carried out at a temperature not lower than the boiling point of the solvent (58 ° C. in the case of HFIP). When HFIP is used, it is preferable to use a hot air circulation type dryer in order to remove HFIP vapor having a higher specific gravity than air from the sample surface.

The means for analyzing the solution of the resin (a) is not particularly limited. For the purpose of knowing the state of deterioration of the resin (a) due to heating during molding, measurement of the solution viscosity, GPC
Various analytical means such as measurement of molecular weight, oligomer analysis, and measurement of the amount of functional group such as acid value and amine value can be adopted.

When the resin (a) has a property of causing cross-linking due to heat deterioration, as a means for easily knowing the state of deterioration due to heat, insoluble resin (a) in the resin (a) solution is used. There is a method of measuring the physical quantity. Specifically, this method can be carried out by filtration of the resin (a) solution and subsequent measurement of the amount of insoluble matter filtered off.
This method is one of the consequences of resin (a) degradation,
The phenomenon that cross-linking occurs and becomes insoluble in the above-mentioned solvent is used. If an insoluble matter is recognized by this analysis, it becomes one proof that the resin laminate, particularly the resin (a) has undergone thermal deterioration, and the amount of the amount serves as a standard for comparing the magnitude of the thermal deterioration. Surprisingly, when resin (a) is a polyamide resin and resin (b) is a fluororesin,
It has been found that there is a correlation between the amount of insoluble matter of the polyamide resin and the degree of change with time of the adhesive strength between layers of the resin laminate.

On the other hand, when the resin (a) has a property of decomposing due to heat deterioration, as a means for easily knowing the state of deterioration due to heat, the molecular weight distribution of the resin (a) is determined using GPC or the like. Is measured. If the analysis shows that the ratio of the presence of low molecular weight increases or the average molecular weight decreases, this is one of the evidences that the resin laminate, especially the resin (a), has been thermally degraded, And the degree of decrease in molecular weight is a measure for comparing the degree of thermal degradation. Further, the long-term reliability of the resin laminate can be determined from the above-described measurement of the magnitude of the thermal deterioration.

The analysis of the laminate sample (resin layer (B)) remaining after the dissolution and removal of the resin layer (A) is not particularly limited, and various means can be adopted according to the purpose. As an example, measurement of tensile strength and tensile elongation of the remaining layer, measurement of crystallinity by X-ray diffraction, specific gravity measurement, heat of crystal fusion measurement, residual stress during molding by polarization microscope observation, heat shrinkage measurement, etc. Measurement and the like. In particular, as an analysis method utilizing the features of the present invention, there is a surface analysis of the surface of the resin layer (B) exposed by dissolving and removing the resin layer (A). Such a surface analysis is performed to measure a change caused by adhesion between the resin layer (A) and the resin layer (B). The above-mentioned change refers to a change caused on the surface of the resin layer (B) or the resin (b) due to the adhesion when comparing the state before the adhesion and the state after the adhesion. Are those described below.

In the conventional method of exposing the surface of the layer constituting the bonding interface by peeling, deformation such as elongation of the layer itself,
And, in part, material destruction was triggered, and subsequent surface analysis resulted in inaccuracies. However, in the removal of the resin layer by dissolution in the present invention, no mechanical force acts on the bonding interface, so that the surface of the layer constituting the bonding interface can be exposed in an ideal state.

As the surface analysis means to be used, any existing surface analysis method can be used. Particularly useful surface analysis methods include (i) ATR-I
R, analysis of surface chemical structure by ESCA, (ii)
ESCA, secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray microanalyzer (EP
MA), analysis of surface elemental composition by X-ray fluorescence analysis,
(Iii) an optical microscope, a scanning electron microscope (SEM),
Surface morphology observation with a scanning tunneling microscope (STM) and a scanning atomic force microscope (AFM). Hereinafter, these three types of analysis methods will be described.

(I) In the ATR-IR method, an IR spectrum near the surface from the sample surface to a depth of about several μm can be obtained. As in the case of the transmission IR spectrum, the qualitative and chemical properties of existing chemical bonds and functional groups can be obtained. Quantitative measurement is possible. ESCA can also know the atomic species existing in the vicinity of the surface from the surface to a depth of about several nm and the bonding state thereof. By using these ATR-IR and ESCA, particularly possible measurements include chemically and / or physically tightly binding to the resin layer (B) exposed by dissolving and removing the resin layer (A). The amount of the resin (a) remaining on the surface of the resin layer (B) without being dissolved even by the dissolving operation, and the amount of the functional group near the surface if any functional group is required for adhesion between the two resin layers Further, if a new chemical bond is formed between the resin layers (A) and (B),
The amount of the chemical bond and the like can be mentioned.

When the resin (a) is a polyamide resin and the resin (b) is a fluororesin, the amount of the polyamide resin remaining on the exposed surface of the fluororesin layer is measured by ATR.
From the -IR measurement, the residual polyamide resin -NHCO-
Can be determined as the ratio of the absorbance of the peak of νC ＝ O near 1645 cm ⁻¹ derived from the peak to the absorbance of the peak characteristic of the fluororesin of the fluororesin layer. From ESCA measurement, it can be determined from the amide bond origin of the residual polyamide resin. It can be determined as a ratio between the peak area of the NH bond and the peak area derived from the fluororesin.

Also, the measurement of the amount of the functional group near the surface of the exposed fluororesin layer is the same as the measurement of the amount of the remaining polyamide resin. The ratio of the absorbance of the characteristic peak of the fluororesin in the fluororesin layer, and from the ESCA measurement, the ratio of the peak area of the characteristic binding mode contained in the functional group to the peak area derived from the fluororesin. be able to. Further, from the change in the obtained amount of the functional group before and after molding, it can be determined whether the molding conditions are appropriate,
It is also a standard for long-term reliability judgment.

(Ii) In the surface elemental analysis by ESCA, secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray microanalyzer (EPMA), X-ray fluorescence analysis, etc., the exposed resin layer (B ) And the number ratio of the elements constituting the surface. The amount of the resin (a) remaining on the exposed surface of the resin layer (B) can be measured also by these surface element analysis means. The resin (a) is a polyamide resin,
When the resin (b) is a fluororesin, the amount of the residual polyamide resin on the exposed surface of the fluororesin layer is determined by the ratio of the number of nitrogen atoms derived from the residual polyamide resin to the number of carbon atoms or fluorine atoms derived from the fluororesin. Can be estimated. These surface analysis means have different analysis depths and sensitivities, and can be properly used according to the purpose and the type of the resin (a) or (b).

(Iii) Observation of the surface morphology by an optical microscope, a scanning electron microscope (SEM), a scanning tunneling microscope (STM), a scanning atomic force microscope (AFM), etc. reveals that the surface of the exposed resin layer (B) Of the resin (a) remaining on the surface of the resin layer (B) from the area ratio between the convex portion and the remaining flat portion. The quantity can be estimated. Furthermore, surface morphology observations provide a wealth of information on surface irregularities at the bonding interface during molding and the presence of holes and the like originating from the generated gas. Becomes possible.

Next, the manufacturing method of the present invention will be described. The method for producing a resin laminate according to the present invention includes at least two steps of (1) molding a resin laminate, and (2) extracting a part of the resin laminate and analyzing the extracted resin laminate by the above method. Consists of

Among them, the molding step (1) of the resin laminate is not particularly limited, and any of the conventional methods can be employed. Some examples of a method for molding a resin laminate and conditions of a fluororesin suitable for the molding method are described below, but the present invention is not particularly limited by the description.

(I) A case in which a laminate in which two layers of a polyamide resin layer and a fluororesin layer are adhered by melt coextrusion molding. Since the extrusion molding is performed simultaneously with the polyamide resin layer, the melting point of the fluororesin forming the fluororesin layer is 160 to 270.
C. is preferred. More preferably, 160-2
30 ° C. In order to make the adhesive strength stronger, a functional group capable of causing chemical and / or physical adhesion by contact with the polyamide resin layer during co-extrusion molding; polarity is induced by an amide bond in the polyamide resin. Such a molecular structure is preferably contained in the fluororesin forming the fluororesin layer. Such functional groups include carboxyl groups, carboxylic acid metal salts, carboxylic anhydrides, acid halides, carbonate groups, hydroxyl groups, epoxy groups, sulfonic acid groups, acid amide groups, double bonds, And a functional group that is converted into a functional group of At this time, these functional groups are
It may be present in any of the main chains. Regarding the molecular weight of the fluororesin, the fluororesin can be molded at a temperature not higher than the thermal decomposition temperature,
In addition, it is preferable that the obtained molded body is in a range where the excellent chemical resistance inherent to the fluororesin, the barrier property against various chemical solutions, the antifouling property and the like can be exhibited. Specifically, the melt flow rate (MFR) is an index of the molecular weight, and the MFR at an arbitrary temperature in the range of about 230 to 350 ° C., which is a general molding temperature range of a fluororesin, is 0.5 to 100 g / 1.
Preferably, it is 0 minutes.

(II) Forming a polyamide resin layer by extrusion on the preformed fluororesin layer,
When obtaining a laminate in which the layers are directly adhered. Generally, the surface of the fluororesin layer is activated by treating the surface of the fluororesin layer with a metal sodium complex solution treatment, corona discharge, plasma etching, etc., and then extruding the polyamide resin layer thereon. There is a way to do it. In this case, the type of the fluororesin forming the fluororesin layer is not particularly limited. It is not particularly necessary to contain a functional group or the like.

(III) The case where the fluororesin layer and the polyamide layer separately formed in advance are heat-sealed or bonded via an adhesive. In order to react with the polyamide layer at the time of heat fusion or to increase the affinity, a functional group may be arranged on the fluororesin as in (I), or the fluororesin layer may be disposed as in (II). The surface may be surface-treated. In addition, when bonding via an adhesive, the surface free energy of the surface of the fluororesin is generally low and the adhesion to the adhesive is unlikely to occur. May be provided, the surface of the fluororesin layer may be surface-treated as in (II), or the surface may be roughened by a physical method such as blasting.

[0040]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples below, but the present invention is not limited to only these Examples.

Example of synthesisPreparation of modified ETFE pellets  ETFE [tetrafluoroethylene / ethylene / (per
(Fluorobutyl) ethylene = 52 / 46.5 / 1.5
(Molar ratio) powder 100 parts, maleic anhydride 1.5 parts
(Parts by weight) and 1.5 parts of dicumyl peroxide.
Pre-mix evenly and use a twin-screw extruder for 300
Modified E by melting and mixing at 2 ° C and average residence time
A TFE pellet was obtained. Cold the obtained pellet
When pressed and measured for FT-IR, 1792 cm
^-1Shows one major peak.

Molding Example 1Molding of multi-layer tube (1)  A co-extruder equipped with two types of two-layer feed block dies
The inner layer / outer layer was used, and the inner diameter was 6 mm.
Product whose outer layer thickness is 0.2mm / 0.8mm respectively
A layer tube was formed. Obtained in the synthesis example in the extruder for the inner layer
The pellets are supplied, and nylon 12 (U) is supplied to the extruder for the outer layer.
3035 MI1 manufactured by Kobe Industries Co., Ltd. was supplied. Modification E
Processing of TFE and nylon 12 at cylinder temperature
The temperatures are 240 ° C and 260 ° C, respectively, and the die temperature is
260 ° C. Tube obtained two-layer laminated tube
-A.

Molding Example 2Lamination of multilayer tube (2)  Except that the cylinder temperature of the modified ETFE was set to 300 ° C.
In the same manner as in Molding Example 1, a two-layer laminated tube was formed.
(Tube-B).

Molding Example 3Lamination of multilayer tube (3)  Except that the cylinder temperature of nylon 12 was set to 290 ° C
In the same manner as in Molding Example 1, a two-layer laminated tube was formed.
Shaped (Tube-C).

Test Example 1Adhesive peel test of multilayer tube  Cut a 1cm wide test piece from the tube and
At a speed of 25 mm / min, 18
Perform a 0 ° peel test and obtain the elongation-tensile strength graph.
The average of the maximum 5 points obtained was determined as the adhesive strength between the layers. this
As a result of the test, adhesive peeling of each tube immediately after tube molding
The strength was found to be as follows. Tube-A: 31 N / cm Tube-B: 8 N / cm (no adhesion) Tube-C: 20 N / cm (practical level or higher)

Test Example 2Long-term fuel filling test of multilayer tube
Trial  Cut the tube to a length of 30 cm and put the simulated fuel CM in the tube.
15 (toluene: isooctane: methanol = 42.
5: 42.5: 15% by volume of a mixed solvent).
Sealed with Swagelok (manufactured by Swagelok)
After that, it was allowed to stand still in a 60 ° C.
After drying out, the adhesive peel strength was measured in the same manner as in Test Example 1.
It was measured. The simulated fuel in the tube has been reduced little by little.
As it went, I replaced it with fresh one every week. This
Test results show that each tube is debonded after long-term fuel filling
The strength was found to be as follows. Tube-A: 28 N / cm (no effect due to fuel filling)
Tube-B: Easy peeling by hand, impossible to measure Tube-C: 10 N / cm (fuel-filled, adhesive peeling strength
Degrees down)

OperationDissolution of outer layer of tube  Tubes A and B are cut into appropriate lengths, and each is sealed.
Placed in HFIP in possible thick glass bottles. Sealed
Rotate on a tabletop ball mill at room temperature to dissolve
Was. Replace HFIP 4 times during 3 days, completely out of layer
Of nylon 12 was dissolved. After that, the tube piece is
Remove from FIP, wash with acetone, dry with hot air circulation
It was dried in a dryer at 100 ° C. for 12 hours. Of molding examples 1-3
Samples obtained by dissolving the tubes were used as samples A
To C.

Embodiment 1Analysis by ATR-IR  FTIR Spectrometer 1760X (Perkin-L)
Angle adjustable ATR attachment (Park)
Nelmer) and set the par with high-purity nitrogen gas.
Samples A to C using a germanium prism
ATR-IR spectrum of the exposed ETFE surface
It was measured. As a result, the ATR-IR scans of Samples A and C
In the vector, one derived from the amide bond of the nylon 12 main chain
640cm^-1Peak and male grafted to ETFE
1792cm derived from formic acid^-1Peak was observed
However, for sample B, 1640 cm^-1The peak of
1792cm^-1Was not observed. This
This means that among the extrusion conditions for obtaining tube B,
Due to the high molding temperature of the layer extruder, adhesive functional groups
Maleic anhydride is decomposed and does not adhere
It became clear that it was.

Embodiment 2Surface observation by SEM  SEM observation of exposed ETFE surface of samples A to C
Using a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.)
It was carried out using. Magnification is 1,000 to 30,000 times
And As a result of observation, it was found that sample A
Probable, convex structures are scattered, other parts
Had a smooth surface without holes. Sample C
In the same manner as in Sample A, convex structures were scattered.
Other parts have a diameter of about 1 to 2 micrometers.
Slight dents were seen. However, in sample B,
The presence of the convex structure seen in pulls A and C was not recognized,
Several holes with a diameter of several micrometers were seen. this
The hole is one of the extrusion conditions of the tube-B, in particular, the pressing of the inner layer.
Adhesive functional group due to high molding temperature
Maleic anhydride decomposed and released gas at the bonding interface
It was expected that it could be done. Gas generated in large quantities
For this reason, it was considered that the adhesion was inhibited. Also, Sun
The dents seen in Pull C are also found when forming Tube-C.
Due to the high molding temperature of the outer layer extruder, nylon
It is considered that decomposition gas was generated from
I got it.

Embodiment 3In nylon 12 / HFIP solution
Of insoluble matter content  HFI of the nylon 12 obtained after dissolution in Example 1.
The P solution was filtered using filter paper, and the solid matter on the filter paper was
Dry at 0 ° C. for 12 hours. After drying, weigh and in HFIP
Calculate the weight ratio to the total amount of nylon 12 melted
Was. Tube-A: 0 wt% Tube-B: 0 wt% Tube-C: 0.8 wt% From these results, the configuration of the outer layer extruder at the time of forming the tube-C was obtained.
Because the molding temperature was high, nylon 12
It turned out that a bridge was made. Also, from this,
The remarkable decrease in adhesive peel strength after initial fuel filling
12 was also found to be due to deterioration.

[0051]

According to the present invention, since the present invention has the above-described structure, it is possible to inspect a product of a resin laminate composed of two kinds of different resins and to clarify the cause of a defect associated therewith, and to achieve long-term reliability of the resin laminate. Can be determined.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Taketo Kato 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Tomohiro Kino 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Inside Yodogawa Manufacturing Co., Ltd.

Claims (10)

[Claims] 1. A resin laminate having a resin layer (A) made of a resin (a) and a resin layer (B) made of a resin (b) of a different type from the resin (a) is formed by a resin (a) ) Is exposed to a solvent that can selectively dissolve
A method for inspecting a resin laminate, characterized by analyzing the remaining resin layer (B) after selectively dissolving and removing the resin (a). 2. The inspection method according to claim 1, wherein the analysis of the remaining resin layer (B) is an analysis of an exposed surface of the resin layer (B). 3. Analysis of the surface of the exposed resin layer (B)
3. The inspection method according to claim 2, wherein the inspection is performed by measuring a change caused by adhesion between the resin layer (A) and the resin layer (B). 4. Analysis of the surface of the exposed resin layer (B)
The inspection method according to claim 3, wherein the inspection is performed by measuring a residual amount of the resin (a) on the surface. 5. An analysis means for analyzing the chemical structure of the surface of the resin layer (B) when analyzing the surface of the resin layer (B) exposed by dissolving and removing the resin (a),
(Ii) analysis means for analyzing the elemental composition of the surface of the resin layer (B), and (iii) analysis means for observing the morphology of the surface of the resin layer (B). The inspection method according to any one of claims 1 to 4, wherein one type of analysis means is used. 6. A resin laminate having a resin layer (A) made of a resin (a) and a resin layer (B) made of a resin (b) of a type different from the resin (a), ) Is exposed to a solvent that can selectively dissolve
A method for inspecting a resin laminate, characterized in that a resin (a) is selectively dissolved to obtain a solution of the resin (a), and then the solution is analyzed. 7. The inspection method according to claim 6, wherein the analysis of the solution is performed by measuring an amount of an insoluble content of the resin (a) contained in the solution. 8. The resin according to claim 1, wherein the resin (a) is a polyamide resin, and the resin (b) is a fluororesin.
Inspection method described in section. 9. The solvent according to claim 1, wherein the solvent capable of selectively dissolving the resin (a) is 1,1,1,3,3,3-hexafluoro-2-propanol. Inspection method described in section. 10. A method for producing a resin laminate having a resin layer (A) composed of a resin (a) and a resin layer (B) composed of a resin (b) of a type different from the resin (a). A resin laminate comprising a step of extracting a part of the produced resin laminate during the production process and performing the inspection method according to any one of claims 1 to 9. Manufacturing method.