WO2018123171A1 - 成形品および成形品の製造方法 - Google Patents
成形品および成形品の製造方法 Download PDFInfo
- Publication number
- WO2018123171A1 WO2018123171A1 PCT/JP2017/034700 JP2017034700W WO2018123171A1 WO 2018123171 A1 WO2018123171 A1 WO 2018123171A1 JP 2017034700 W JP2017034700 W JP 2017034700W WO 2018123171 A1 WO2018123171 A1 WO 2018123171A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- casing
- polyamide resin
- housing
- resin
- melting point
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000465 moulding Methods 0.000 title abstract description 20
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 124
- 238000002844 melting Methods 0.000 claims abstract description 62
- 230000008018 melting Effects 0.000 claims abstract description 62
- 239000011342 resin composition Substances 0.000 claims abstract description 52
- 238000002425 crystallisation Methods 0.000 claims abstract description 46
- 230000008025 crystallization Effects 0.000 claims abstract description 28
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- 238000005375 photometry Methods 0.000 claims abstract description 4
- 238000003466 welding Methods 0.000 claims description 39
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 21
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- 239000000945 filler Substances 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 abstract description 59
- 239000011347 resin Substances 0.000 abstract description 59
- 238000009833 condensation Methods 0.000 abstract description 12
- 230000005494 condensation Effects 0.000 abstract description 12
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- -1 Aliphatic diamines Chemical class 0.000 description 15
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 238000005304 joining Methods 0.000 description 10
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- 238000001746 injection moulding Methods 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
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- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
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- B29C66/7377—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline
- B29C66/73773—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being semi-crystalline
- B29C66/73774—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined amorphous, semi-crystalline or crystalline the to-be-joined area of at least one of the parts to be joined being semi-crystalline the to-be-joined areas of both parts to be joined being semi-crystalline
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- B29D11/00—Producing optical elements, e.g. lenses or prisms
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- G03B17/00—Details of cameras or camera bodies; Accessories therefor
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- G03B17/12—Bodies with means for supporting objectives, supplementary lenses, filters, masks, or turrets
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
- H05K5/02—Details
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- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/16—Laser beams
- B29C65/1629—Laser beams characterised by the way of heating the interface
- B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
- G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses
- G02B7/022—Mountings, adjusting means, or light-tight connections, for optical elements for lenses lens and mount having complementary engagement means, e.g. screw/thread
Definitions
- the present invention relates to a molded product and a method for manufacturing the molded product.
- the present invention relates to a molded product suitable for camera parts, and a method for manufacturing the molded product.
- Patent Document 1 contains 60 to 100 mol% of a dicarboxylic acid unit containing 60 to 100 mol% of a terephthalic acid unit and 1,9-diaminononane unit and / or 2-methyl-1,8-diaminooctane unit.
- the polyamide (A) having a diamine unit and the fibrous reinforcing material (B) are melt-kneaded and the content of the polyamide (A) is 50 to 80% by mass, and the content of the fibrous reinforcing material (B) is A barrel or holder of a camera module formed by molding a polyamide composition of 20 to 50% by mass, the barrel of the camera module having an average length of 300 ⁇ m or less before melt-kneading of the fibrous reinforcing material (B) Or a holder is disclosed.
- the laser transmission welding method is a resin member (hereinafter also referred to as “transmission resin member”) that is transparent (also referred to as non-absorbing or weakly absorbing) to laser light, and absorbable to laser light.
- transmission resin member a resin member (hereinafter sometimes referred to as an “absorbing resin member”) having a contact is welded to be bonded to each other.
- absorbing resin member a resin member having a contact is welded to be bonded to each other.
- the joining surface is irradiated with laser light from the side of the transmissive resin member, and the absorbing resin member forming the joining surface is melted and joined by the energy of the laser light.
- the camera component 5 includes a plurality of resin lens holders 2 that hold the lens unit 1, a connector 3, and a resin case 4 that holds the connector. Consists of parts.
- the lens unit 1 is normally held by a resin lens holder, and the connector 3 is held by a resin case 4 that holds the connector, and then the resin lens holder 2 and the connector. It is manufactured by bonding a resin case 4 that holds
- both the lens holder 2 and the case 4 holding the connector are made of resin, they can be joined by a welding technique such as laser welding, but at the time of joining, they are joined to the joining interface (dotted line portion in FIG. 1). There may be a gap.
- An object of the present invention is to solve such a problem, and includes a first housing made of resin, a second housing joined to the first housing made of resin, In the molded product having the transparent member held in the housing 2, no condensation or fogging occurs in the transparent member, and the appearance of the joint portion between the first housing and the second housing is good. And it aims at providing the manufacturing method of the said molded article.
- the casings are slowly joined together by using a polyamide resin having a melting point of the polyamide resin + 20 ° C. and a semi-crystallization time of 10 to 60 seconds.
- the present invention has been completed by successfully reducing the gap between the casings.
- the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 11>.
- the body and the second casing are each independently formed from a resin composition containing a polyamide resin having a polyamide resin semi-crystallization time of 10 to 60 seconds and a melting point of 200 to 280 ° C., Molded product in which the transparent member has a pencil hardness of 8H or more and a linear expansion coefficient of 1 ⁇ 10 ⁇ 6 to 9 ⁇ 10 ⁇ 6 / ° C .; the semi-crystallization time is the melting point of the polyamide resin + 20 ° C., the polyamide resin The time measured by depolarization photometry under the conditions of a melting time of 5 minutes and a crystallization bath temperature of 150 ° C.
- the polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, 50 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine, and the structural unit derived from the dicarboxylic acid
- ⁇ 3> The molded article according to ⁇ 1> or ⁇ 2>, wherein a difference in melting point between the polyamide resin contained in the first housing and the polyamide resin contained in the second housing is 50 ° C. or less.
- ⁇ 4> The molded article according to any one of ⁇ 1> to ⁇ 3>, wherein the first casing and the second casing each independently include a filler.
- One of the first casing and the second casing includes a light-absorbing dye, and the other one includes a light-transmitting dye, and any one of ⁇ 1> to ⁇ 4> Articles described in 1.
- ⁇ 6> The molded article according to any one of ⁇ 1> to ⁇ 5>, wherein the transparent member is made of glass.
- ⁇ 7> The molded product according to any one of ⁇ 1> to ⁇ 6>, which is a camera part.
- each of the bodies is independently formed of a resin composition containing a polyamide resin having a polyamide resin semi-crystallization time of 10 to 60 seconds and a melting point of 200 to 280 ° C., and the transparent member has a pencil hardness of 8H or more.
- One of the first casing and the second casing includes a light-absorbing dye, and the remaining one of the molded article according to ⁇ 8> or ⁇ 9> includes a light-transmitting dye. Production method.
- ⁇ 11> Any one of ⁇ 8> to ⁇ 10>, wherein a difference in melting point between the polyamide resin included in the first casing and the polyamide resin included in the second casing is 50 ° C. or less.
- a transparent member In a molded article having a first housing made of resin, a second housing joined to the first housing made of resin, and a transparent member held by the second housing, a transparent member.
- the molded product of the present invention includes a first housing, a second housing joined to the first housing, and a transparent member held by the second housing,
- the first casing and the second casing are each independently made of a resin composition containing a polyamide resin having a polyamide resin semi-crystallization time of 10 to 60 seconds and a melting point of 200 to 280 ° C.
- the transparent member is formed and has a pencil hardness of 8H or more and a linear expansion coefficient of 1 ⁇ 10 ⁇ 6 to 9 ⁇ 10 ⁇ 6 / ° C.
- the semi-crystallization time means the time measured by the depolarization photometric method under the conditions of the melting point of the polyamide resin + 20 ° C., the melting time of the polyamide resin of 5 minutes, and the crystallization bath temperature of 150 ° C.
- the heat welding can be slowly advanced at the time of joining the first housing and the second housing. And the gap at the interface of the second housing can be reduced. For this reason, moisture or the like is less likely to enter the molded product obtained by joining the first housing and the second housing, so that condensation does not easily occur on the transparent member and clouding is less likely to occur.
- the molded product of the present invention can be applied to various storage containers having transparent members, electrical and electronic equipment parts, office automate (OA) equipment parts, home appliance parts, machine mechanism parts, vehicle mechanism parts, and the like.
- the molded article of the present invention is preferably a camera part, and more preferably a vehicle-mounted camera part.
- the depolarized intensity method is a method for measuring the progress of crystallization of a resin by utilizing a phenomenon in which light transmitted through the resin due to crystallization causes birefringence.
- the amount of light transmitted through the polarizing plate increases in proportion to the degree of progress of crystallization.
- the amount of transmitted light (transmitted light intensity) is measured by a light receiving element.
- the semi-crystallization time is that after the resin is in an amorphous state or a molten state, the transmitted light intensity is (I ⁇ I0) / 2 (I0 is the transmitted light intensity in the amorphous state or the molten state, and I ⁇ is constant. This represents a time required to reach a value), that is, a time required for crystallization to proceed in half, and serves as an index of crystallization speed.
- the depolarization intensity method is measured in accordance with the description of the examples described later.
- the molded article of the present invention usually further includes one or more members.
- An example of the member is a camera component connector.
- the molded article of the present invention preferably has a hollow structure separated from the outside and formed by at least a first casing, a second casing, and a transparent member.
- the camera component 5 in FIG. 1 includes a resin case 4 (corresponding to a first housing) holding a connector, a resin lens holder 2 (corresponding to a second housing), and a lens unit 1 (transparent).
- a hollow structure for holding the connector 3 is formed. Further, the hollow structure is not necessarily formed only by the first casing, the second casing, and the transparent member.
- the molded product of the present invention may include a third housing and a member and a hollow structure separated from the outside.
- the third housing is also preferably formed from a resin composition containing a polyamide resin that satisfies the predetermined crystallization speed and melting point. The higher the degree of sealing of the hollow structure, the more effectively the fogging and condensation of the transparent member can be suppressed.
- the first casing and the second casing are each independently formed from a resin composition.
- the resin composition used for forming the first housing and the resin composition used for forming the second housing may be the same or different.
- the resin composition used for forming the first casing and the resin composition used for forming the second casing have a common composition of 80% by mass or more and less than 100% by mass.
- the resin composition forming one of the first casing and the second casing and the resin composition forming the other have 80 to 100% by mass of the polyamide resin component in common.
- casing contains a light absorptive pigment
- the resin composition forming the other casing contains a light-transmitting dye.
- the method for producing the resin composition is not particularly limited, but a method of using a uniaxial or biaxial extruder having equipment capable of devolatilization from the vent port as a kneader is preferable.
- the polyamide resin and other components blended as necessary may be supplied to the kneader all at once, or other blended components may be sequentially supplied to the polyamide resin component.
- the filler is preferably supplied from the middle of the extruder in order to suppress crushing during kneading.
- two or more kinds of components selected from each component may be mixed and kneaded in advance.
- the light-transmitting dye is prepared in advance as a master batch, melt-kneaded with the remaining blending components, and extruded to have a predetermined blending ratio.
- the first casing and the second casing are formed from a resin composition, but the molding method is not particularly limited, and can be molded by a molding method generally used for thermoplastic resins. Specifically, a molding method such as injection molding, hollow molding, extrusion molding, or press molding can be applied. In this case, a particularly preferable molding method is injection molding because of good fluidity. In the injection molding, the resin temperature is preferably controlled to 240 to 300 ° C.
- the polyamide resin used in the present invention is a polyamide resin having a semi-crystallization time of 10 to 60 seconds and a melting point of 200 to 280 ° C. By setting it as the said range, since the softening time is long at the time of welding, joint strength improves. When the half crystallization time is less than 10 seconds, the resin solidifies quickly, and appropriate adhesion strength cannot be obtained. In addition, when the half crystallization time exceeds 60 seconds, the resin is soft and it is difficult to apply an appropriate pressure during bonding.
- the semi-crystallization time of the polyamide resin is measured according to the method described in Examples described later.
- the resin composition used in the present invention may contain only one type of polyamide resin or two or more types.
- the half crystallization time of the polyamide resin with the largest blending amount is defined as the half crystallization time of the polyamide resin in the present invention.
- the lower half value of the polyamide resin contained in the first housing and the polyamide resin contained in the second housing is independently 10 seconds or more and 20 seconds or more. Preferably, it is 25 seconds or more, and more preferably 30 seconds or more.
- the upper limit value of the half crystallization time is independently 60 seconds or less, preferably 55 seconds or less, more preferably 50 seconds or less, and further preferably 45 seconds or less. By setting it as such a range, the welding intensity
- the polyamide resin used in the present invention has a melting point of 200 to 280 ° C.
- the lower limit of the melting point is preferably 205 ° C. or higher, and more preferably 210 ° C. or higher.
- the upper limit of the melting point is preferably 260 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 240 ° C. or lower.
- the melting point of the polyamide resin is measured according to the method described in Examples described later.
- the melting point of the polyamide resin having the largest blending amount is defined as the melting point of the polyamide resin in the present invention.
- the polyamide resin has two or more melting points, the lowest melting point is defined as the melting point of the polyamide resin in the present invention.
- the difference in melting point between the polyamide resin contained in the first housing and the polyamide resin contained in the second housing is preferably 50 ° C. or less, and more preferably 30 ° C. or less. 20 ° C. or lower is more preferable, 10 ° C.
- casing can be decreased more.
- the difference in melting point is preferably 0 ° C.
- the polyamide resin used in the present invention satisfies the above-mentioned half crystallization time and melting point, the kind thereof is not particularly defined, and widely known polyamide resins can be used.
- the polyamide resin used in the present invention is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, and 50 mol% or more of the structural unit derived from a diamine is derived from xylylenediamine, and is derived from a dicarboxylic acid.
- 70 mol% or more of the unit is a polyamide resin derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter sometimes referred to as “XD polyamide”).
- the XD-based polyamide is composed of 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, more preferably 95 mol% or more of diamine-derived structural units. (Preferably at least one of metaxylylenediamine and paraxylylenediamine), 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of the structural unit derived from dicarboxylic acid, Preferably 90 mol%, more preferably 95 mol% or more is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
- the XD polyamide used in the present invention is preferably 30 mol% or more, more preferably 50 mol% or more, and still more preferably 60 mol% or more of the structural unit derived from diamine is metaxylylenediamine.
- diamines other than metaxylylenediamine and paraxylylenediamine that can be used as raw material diamine components for XD polyamides include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, Aliphatic diamines such as methylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (amino Methyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis ( --Aminocyclohexyl) propane, bis ( --
- diamine other than xylylenediamine When a diamine other than xylylenediamine is used as the diamine component, it is less than 50 mol% of the structural unit derived from diamine, preferably 30 mol% or less, more preferably 1 to 25 mol%, still more preferably. Used in a proportion of 5 to 20 mol%.
- Preferred examples of the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms to be used as the raw material dicarboxylic acid component of the polyamide resin include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, Examples thereof include aliphatic dicarboxylic acids such as sebacic acid, undecanedioic acid, and dodecanedioic acid, and one or a mixture of two or more types can be used.
- the melting point of the polyamide resin is an appropriate range for molding processing Therefore, adipic acid or sebacic acid is preferable, and sebacic acid is more preferable.
- dicarboxylic acid component other than the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms examples include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3 -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene
- naphthalenedicarboxylic acid compounds such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and one kind or a mixture of two or more kinds can be used.
- a dicarboxylic acid other than an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component
- at least one of terephthalic acid and isophthalic acid is used from the viewpoint of molding processability and barrier properties. It is preferable to use, and it is more preferable to use isophthalic acid.
- the proportion of terephthalic acid and isophthalic acid is preferably 30 mol% or less, more preferably 1 to 30 mol%, still more preferably 5 to 20 mol% of the dicarboxylic acid structural unit. Details of these can be referred to the description in JP-A-2005-002327.
- lactams such as ⁇ -caprolactam and laurolactam
- aliphatics such as aminocaproic acid and aminoundecanoic acid, as long as the effects of the present invention are not impaired.
- Aminocarboxylic acids can also be used as copolymerization components.
- Preferred polyamide resins used in the present invention include polyamide resin (MXD6I) composed of metaxylylenediamine, adipic acid and isophthalic acid, polyamide resin (MXD6) composed of metaxylylenediamine and adipic acid, metaxylylene diene Polyamide resin composed of amine, paraxylylenediamine and adipic acid (MP6), Polyamide resin composed of metaxylylenediamine and sebacic acid (MXD10), composed of metaxylylenediamine, paraxylylenediamine and sebacic acid An example is a polyamide resin (MP10).
- the polyamide resin used in the present invention preferably has a number average molecular weight (Mn) of 6,000 to 30,000, more preferably 8,000 to 28,000, and still more preferably 9,000 to 26,000. 000, more preferably 10,000 to 24,000, and even more preferably 11,000 to 22,000. Within such a range, the heat resistance, elastic modulus, dimensional stability, and moldability become better.
- Mn number average molecular weight
- the polyamide resin used in the present invention preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of 1.8 to 3.1.
- the molecular weight distribution is more preferably 1.9 to 3.0, still more preferably 2.0 to 2.9.
- the molecular weight distribution of the polyamide resin can be adjusted, for example, by appropriately selecting the polymerization reaction conditions such as the type and amount of the initiator and catalyst used during the polymerization, and the reaction temperature, pressure, and time. It can also be adjusted by mixing a plurality of types of polyamide resins having different average molecular weights obtained under different polymerization conditions or by separately precipitating the polyamide resins after polymerization.
- the molecular weight distribution can be obtained by GPC measurement. Specifically, using “HLC-8320GPC” manufactured by Tosoh Corporation as an apparatus and two “TSK gel Super HM-H” manufactured by Tosoh Corporation as a column, eluent Measured under conditions of hexafluoroisopropanol (HFIP) having a sodium trifluoroacetate concentration of 10 mmol / L, a resin concentration of 0.02% by mass, a column temperature of 40 ° C., a flow rate of 0.3 mL / min, and a refractive index detector (RI). It can be determined as a value in terms of polymethyl methacrylate (PMMA). A calibration curve is prepared by dissolving 6 levels of PMMA in HFIP.
- HFIP hexafluoroisopropanol
- the polyamide resin used in the present invention has a moisture permeability coefficient of 3.0 g ⁇ mm / day ⁇ m 2 or less after being molded to a thickness of 1 mm and left to stand at 40 ° C. and a relative humidity of 90% for 40 hours.
- the lower limit value of the moisture permeability coefficient is preferably 0 g ⁇ mm / day ⁇ m 2 , but 0.1 g ⁇ mm / day ⁇ m 2 or more, or even 1.0 g ⁇ mm / day ⁇ m 2 or more. It is sufficiently practical.
- the moisture permeability coefficient is a value measured by the method described in the examples. Even if the water absorption rate of the polyamide resin is low, it cannot be said that the moisture permeability coefficient is small. This is because the polyamide resin has a different water absorption rate and diffusion rate.
- the resin composition used in the present invention preferably contains 25% by mass or more, and more preferably 30% by mass or more of the polyamide resin. As an upper limit, it is less than 100 mass%, 90 mass% or less is preferable, 70 mass% or less is more preferable, and 60 mass% or less is further more preferable.
- the resin composition used in the present invention preferably occupies 90% by mass or more of the total of the polyamide resin and the filler described later.
- the resin composition used in the present invention may contain one or more polyamide resins other than those described above.
- polyamide resins include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (Polyamide 6I), polyamide 66 / 6T, polyamide 9MT, polyamide 6I / 6T and the like.
- polyamide resins are not substantially contained.
- “Substantially not contained” means that, in the resin composition used in the present invention, it means 2% by mass or less of the content of the polyamide resin satisfying the predetermined crystallization rate and the melting point, preferably 1% by mass or less, 0.1 mass% or less is more preferable.
- the resin composition used in the present invention may contain a filler.
- the filler may be an organic filler or an inorganic filler, but an inorganic filler is preferred.
- the inorganic filler include glass fillers, carbon fibers, silica, alumina, and fillers that can absorb laser light such as inorganic powders coated with a material that absorbs lasers, glass fillers are preferable, and glass fibers are more preferable.
- the glass filler is composed of a glass composition such as A glass, C glass, E glass, or S glass, and E glass (non-alkali glass) is particularly preferable.
- the glass fiber used in the present invention may be a single fiber or a plurality of single fibers twisted together.
- the form of the glass fiber is “glass roving” in which single fibers or a plurality of twisted strands are continuously wound, “chopped strand” trimmed to a length of 1 to 10 mm, and pulverized to a length of about 10 to 500 ⁇ m. Any of "Mildo fiber” etc. may be sufficient.
- Such glass fibers are commercially available from Asahi Fiber Glass Co., Ltd. under the trade names “Glasslon Chopped Strand” and “Glasslon Milled Fiber”, and are easily available.
- glass fibers having an irregular cross-sectional shape are also preferable.
- This irregular cross-sectional shape means that the flatness indicated by the long diameter / short diameter ratio (D2 / D1) when the long diameter of the cross section perpendicular to the length direction of the fiber is D2 and the short diameter is D1, is, for example, 1. It is preferably 5 to 10, more preferably 2.5 to 10, more preferably 2.5 to 8, and particularly preferably 2.5 to 5. Regarding such flat glass, the description of paragraph numbers 0065 to 0072 of JP-A-2011-195820 can be referred to, and the contents thereof are incorporated herein.
- the glass fiber used in the present invention is particularly preferably a glass fiber having a weight average fiber diameter of 1 to 20 ⁇ m and a cut length of 1 to 10 mm.
- the weight average fiber diameter is calculated as a weight average fiber diameter in a circle having the same area.
- the glass fiber used in the present invention may be bundled with a sizing agent. In this case, an acid-based sizing agent is preferable as the sizing agent.
- the glass filler in the present invention may be glass beads.
- the glass beads are spherical ones having an outer diameter of 10 to 100 ⁇ m.
- they are commercially available from Potters Barotini under the trade name “EGB731” and can be easily obtained.
- Glass flakes are flakes having a thickness of 1 to 20 ⁇ m and a side length of 0.05 to 1 mm.
- they are commercially available from Nippon Sheet Glass under the trade name “Fureka”. Are readily available.
- the filler content in the resin composition used in the present invention is preferably 25% by mass or more of the resin composition, and more preferably 30% by mass or more. About an upper limit, 70 mass% or less is preferable, 65 mass% or less is more preferable, 60 mass% or less is more preferable, 55 mass% or less is still more preferable, 50 mass% or less is still more preferable, 45 mass% or less is 45 mass% or less. Even more preferred.
- the resin composition used in the present invention may contain only one type of filler, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- One of the resin compositions used in the present invention preferably contains a light-absorbing dye. With this configuration, laser welding can be performed.
- the other of the resin compositions used in the present invention may contain a light-transmitting dye. By including the light-transmitting dye, the first casing and the second casing can be more strongly laser-welded.
- the light-absorbing dye examples include those having an absorption wavelength in the range of the wavelength of the laser beam to be irradiated, for example, in the wavelength range of 800 nm to 1100 nm.
- inorganic pigments black pigments such as carbon black (eg, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black), red pigments such as iron oxide red, molybdate orange, etc.
- inorganic pigments generally have a strong hiding power and are preferably black pigments.
- These light absorbing dyes may be used in combination of two or more. When blended, the amount of the light-absorbing dye is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the resin composition.
- the light transmissive dye is a dye having a high transmittance in the range of the wavelength of the laser beam to be irradiated, for example, in the wavelength range of 800 nm to 1100 nm.
- Specific examples include nigrosine, perinone, naphthalocyanine, aniline black, phthalocyanine, porphyrin, perylene, quaterylene, azo dye, anthraquinone, squaric acid derivative, and immonium dye.
- Examples of commercially available products include e-BIND LTW-8931H and e-BIND LTW-8701H, which are colorants manufactured by Orient Chemical Industries.
- the content of the light transmissive pigment is preferably 0.001% by mass or more, more preferably 0.006% by mass or more, and further 0.018% by mass of the resin composition. As mentioned above, it may be 0.024 mass% or more, 0.030 mass% or more, or 0.050 mass% or more.
- the upper limit is preferably 5.0% by mass or less, more preferably 2.0% by mass or less, further preferably 1.0% by mass or less, 0.2% by mass or less, It may be 0.1% by mass or less and 0.06% by mass or less.
- the light-transmitting dye may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.
- the resin composition used in the present invention may contain one or more resin components other than the polyamide resin.
- polyester resins such as polyethylene terephthalate and polybutylene terephthalate
- thermoplastic resins such as polycarbonate resin and polyacetal resin
- the resin composition used in the present invention may have a configuration in which a resin component other than the polyamide resin is not substantially blended. In particular, it may be 0.4% by mass or less.
- the resin composition used in the present invention may contain talc.
- crystallization can be promoted by blending talc.
- the blending amount of talc in the resin composition used in the present invention is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the resin composition.
- the content is more preferably 15 to 5% by mass, and further preferably 0.2 to 1.0% by mass.
- Only one type of talc may be used, or two or more types may be used in combination. In the case of two or more types, the total amount is preferably within the above range.
- the resin composition used in the present invention may contain a release agent.
- the release agent include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. Etc.
- the aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids.
- the aliphatic carboxylic acid includes alicyclic carboxylic acid.
- preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred.
- aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetratriacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.
- the salt of the aliphatic carboxylic acid include sodium salt, potassium salt, calcium salt, and magnesium salt.
- the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol for example, the same one as the aliphatic carboxylic acid can be used.
- the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic or alicyclic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable.
- alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, trimethylolpropane, ditrimethylolpropane, And dipentaerythritol.
- esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
- esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
- examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastea
- Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
- the aliphatic hydrocarbon includes alicyclic hydrocarbons.
- the number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
- paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
- the content of the release agent is preferably 0.001 to 2% by mass, and 0.01 to 1% by mass with respect to the resin composition. More preferably. Only one type of release agent may be used, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.
- the resin composition used in the present invention may contain other components without departing from the spirit of the present invention.
- additives include light stabilizers, antioxidants, flame retardants, UV absorbers, fluorescent brighteners, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, and flow improvers.
- Plasticizers, dispersants, antibacterial agents and the like may use only 1 type and may use 2 or more types together.
- the molded article of the present invention includes a transparent member having a pencil hardness of 8H or more and a linear expansion coefficient of 1 ⁇ 10 ⁇ 6 to 9 ⁇ 10 ⁇ 6 / ° C.
- a transparent member constitutes a lens part of a camera component, for example.
- the pencil hardness of the transparent member is preferably 8H to 9H.
- the pencil hardness is a value measured according to JIS K 5600.
- the linear expansion coefficient of the transparent member is preferably 5 ⁇ 10 ⁇ 6 to 9 ⁇ 10 ⁇ 6 / ° C.
- the linear expansion coefficient is a value measured according to JIS K 7197. Examples of the material of the transparent member include glass and resin, and glass is preferable.
- the transparent member in the present invention is held by the second casing. As an example of being held, a state in which the transparent member is directly or indirectly fitted to the second casing can be given. Indirect fitting means a state of fitting through a member such as packing.
- the method for manufacturing a molded article of the present invention includes welding a first casing and a second casing, the second casing including a first casing holding a transparent member, The second casing holds a transparent member, and the first casing and the second casing are each independently a semi-crystalline polyamide resin.
- a resin composition containing a polyamide resin having a melting time of 10 to 60 seconds and a melting point of 200 to 280 ° C. the difference in melting point is 50 ° C. or less
- the transparent member has a pencil hardness of 8H or more
- the linear expansion coefficient is 1 ⁇ 10 ⁇ 6 to 9 ⁇ 10 ⁇ 6 / ° C.
- the semi-crystallization time is a time measured by a depolarization photometric method under the conditions of a melting point of polyamide resin + 20 ° C., a melting time of polyamide resin of 5 minutes, and a crystallization bath temperature of 150 ° C.
- the first casing, the second casing, the transparent member, and the resin composition can each refer to the description in the molded product, and preferable ranges thereof are also the same.
- the manufacturing method of the present invention includes thermally welding the first casing and the second casing.
- the method of heat welding is not particularly defined as long as it is a method of melting and joining the joining portions of the first housing and the second housing with heat, but laser welding is preferable.
- the temperature for heat welding is determined based on the melting point of the polyamide resin, and is preferably heated to the melting point of the polyamide resin +50 to 300 ° C.
- the melting point of the polyamide resin here is set based on the polyamide resin having the lowest melting point among the polyamide resins included in the first casing and the second casing and satisfying the predetermined crystallization speed and the melting point. .
- the first casing and the second casing can be formed into a molded product by laser welding.
- one of the first housing and the second housing is a transmissive resin member, and the other is an absorbent resin member.
- the transmissive resin member and the absorbing resin member can be firmly welded without using an adhesive.
- the shape of the joining portion between the first housing and the second housing is not particularly limited, but is usually a shape having at least a surface contact portion (a flat surface or a curved surface) because the members are joined together by laser welding. .
- the thickness of the member through which the laser beam is transmitted (the thickness in the laser transmission direction at the portion through which the laser beam is transmitted) can be appropriately determined in consideration of the application, the composition of the resin composition, and the like. Preferably, it is 4 mm or less.
- laser light sources used for laser welding include fiber laser (wavelength 1070 nm), YAG (yttrium, aluminum, garnet crystal) laser (wavelength 1064 nm), and LD (laser diode) (wavelength 808, 840, 940 nm).
- the optimum laser is selected by comprehensively judging the beam quality (heat source), power stability, cost, etc.
- the welded portions are brought into contact with each other.
- surface contact is desirable between the welded portions of the two, and may be flat surfaces, curved surfaces, or a combination of flat and curved surfaces.
- laser light is irradiated from the transmissive resin member side (preferably, the weld surface is irradiated from an angle of 85 to 95 °).
- the laser beam may be condensed at the interface between the two using a lens system if necessary. The condensed beam passes through the transmissive resin member, is absorbed near the surface of the absorbent resin member, generates heat, and melts.
- the heat is transferred to the permeable resin member by heat conduction and melted to form a molten pool at the interface between the two, and after cooling, both are joined.
- the molded product in which the permeable resin member and the absorbent resin member are welded in this way has high bonding strength.
- the obtained polyamide had a melting point of 215 ° C., a glass transition point of 64.4 ° C., a number average molecular weight of 14,286, and a relative viscosity (measured in 96% sulfuric acid, resin concentration 1 g / 100 cc, temperature 25 ° C.) of 2. 0.09, the terminal amino group concentration was 60.0 ⁇ equivalent / g, and the terminal carboxyl group concentration was 80.0 ⁇ equivalent / g.
- PA66 Polyamide 66, manufactured by Toray, trade name “CM3001-N”
- the mass of the calcium chloride particles was measured, and the water permeation coefficient was calculated by taking the difference (increase) from that before standing as the amount of permeated water.
- the unit of the moisture permeability coefficient is g ⁇ mm / day ⁇ m 2 .
- the semi-crystallization time was measured by a depolarization photometric method under the conditions of a melting point of polyamide resin + 20 ° C., a melting time of polyamide resin of 5 minutes, and a crystallization bath temperature of 150 ° C.
- model number: MK701 manufactured by Kotaki Seisakusho Co., Ltd. was used as the semi-crystallization time measuring device. Specifically, a polyamide resin is melted at a melting point of + 20 ° C. using a single screw extruder or the like, and is formed by stacking five sheets of a film having a glass transition temperature of ⁇ 5 ° C. and a chill roll temperature of 100 ⁇ m.
- the unit of half crystallization time is seconds.
- the melting point was measured as the peak top temperature of the endothermic peak at the time of temperature rise observed by DSC (Differential Scanning Calorimetry).
- DSC Different Scanning Calorimetry
- the sample amount was about 1 mg
- nitrogen was flowed at 30 mL / min as the atmospheric gas
- the rate of temperature increase was from room temperature to a temperature higher than the expected melting point at 10 ° C./min.
- the melting point was determined from the temperature at the peak top of the endothermic peak observed when heated and melted.
- DSC-60 manufactured by SHIMADZU CORPORATION was used.
- the unit of melting point is ° C.
- ⁇ Filler> T756H Glass fiber, manufactured by Nippon Electric Glass Co., Ltd., ECS03T-756H (trade name), weight average fiber diameter 10.5 ⁇ m, cut length 3 to 4 mm, ⁇ Light transmissive dye> 8731H: Orient Chemical Industries, Ltd., e-BIND LTW-8731H (trade name), polyamide 66 and light-transmitting dye master batch ⁇ light-absorbing dye> Carbon black (Mitsubishi Chemical Corporation MA600B) ⁇ Talc> Micron White # 5000S: Hayashi Kasei Co., Ltd. ⁇ release agent> Light Amide WH255: Kyoeisha Chemical Co., Ltd.
- Example 1 ⁇ Production of light-transmitting casing> ⁇ Manufacture of resin composition >> The polyamide resin, talc, release agent and light-transmitting dye shown in Table 2 were weighed and dry blended, and then the twin screw type cassette weighing from the screw root of a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS). A feeder (manufactured by Kubota Corporation, CE-W-1-MP) was used. Further, the glass fibers shown in Table 2 were introduced into the above-described twin-screw extruder from the side of the extruder using a vibrating cassette weighing feeder (manufactured by Kubota Corporation, CE-V-1B-MP), and resin components, etc. And kneaded to obtain pellets. The temperature setting of the extruder was 280 ° C.
- the glass fibers shown in Table 3 were introduced into the above twin screw extruder from the side of the extruder using a vibrating cassette weighing feeder (manufactured by Kubota Corporation, CE-V-1B-MP), and the resin components, etc. And kneaded to obtain pellets.
- the temperature setting of the extruder was 280 ° C.
- a glass lens was fitted as a transparent member into the light-transmitting casing obtained above, and laser-welded to the light-absorbing casing.
- the light-transmitting casing and the light-absorbing casing were overlapped, and laser irradiation was performed from the light transmitting casing side.
- the glass lens has a pencil hardness of 8H and a linear expansion coefficient of about 8.5 ⁇ 10 ⁇ 6 .
- the laser beam wavelength was 940 nm (semiconductor laser), the welding spot diameter was 2.0 mm, and the welding length was 20 mm.
- the scanning speed of the laser beam was 5 mm / second, the laser output was 13 W, and the clamp pressure was 0.5 MPa.
- As the laser welding apparatus a PARK LASER SYSTEM manufactured by Scan type Parker Corporation was used.
- Example 2 Comparative Example 1 and Comparative Example 2
- the polyamide resin used for the light-absorbing casing and the light-transmitting casing was changed to the polyamide resin shown in Table 4 below, and the others were performed in the same manner.
- Example 3 ⁇ Production of light-absorbing housing> ⁇ Manufacture of resin composition >> The polyamide resin, talc, release agent, and light-absorbing dye shown in Table 3 were weighed, dry blended, and then twin screw type cassette weighing from the screw root of a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS). A feeder (manufactured by Kubota Corporation, CE-W-1-MP) was used. About the light absorptive pigment
- the glass fibers shown in Table 3 were introduced into the above twin screw extruder from the side of the extruder using a vibrating cassette weighing feeder (manufactured by Kubota Corporation, CE-V-1B-MP), and the resin components, etc. And kneaded to obtain pellets.
- the temperature setting of the extruder was 280 ° C.
- a glass lens was fitted as a transparent member into the light-absorbing casing obtained above, and laser-welded to the light-transmitting casing.
- the light-absorbing casing and the light-transmitting casing were overlapped, and laser irradiation was performed from the light-transmitting casing side.
- the glass lens has a pencil hardness of 8H and a linear expansion coefficient of about 8.5 ⁇ 10 ⁇ 6 .
- the laser beam wavelength was 940 nm (semiconductor laser), the welding spot diameter was 2.0 mm, and the welding length was 20 mm.
- the scanning speed of the laser beam was 5 mm / second, the laser output was 13 W, and the clamp pressure was 0.5 MPa.
- As the laser welding apparatus a PARK LASER SYSTEM manufactured by Scan type Parker Corporation was used.
- the resulting molded product was evaluated in the same manner as in Example 1 for ⁇ cloudiness or condensation> and ⁇ appearance>.
- Example 4 In Example 3, the polyamide resin used for the light-absorbing casing and the light-transmitting casing was changed to the polyamide resin shown in Table 4, and the others were performed in the same manner.
Abstract
Description
例えば、特許文献1には、テレフタル酸単位を60~100モル%含有するジカルボン酸単位と1,9-ジアミノノナン単位および/または2-メチル-1,8-ジアミノオクタン単位を60~100モル%含有するジアミン単位とを有するポリアミド(A)および繊維状強化材(B)を溶融混練してなりポリアミド(A)の含有率が50~80質量%であり繊維状強化材(B)の含有率が20~50質量%であるポリアミド組成物を成形してなるカメラモジュールのバレルまたはホルダであって、上記繊維状強化材(B)の溶融混練前における平均長さが300μm以下であるカメラモジュールのバレルまたはホルダが開示されている。
本発明は、かかる課題を解決することを目的としたものであって、樹脂製の第1の筐体と、樹脂製の第1の筐体と接合している第2の筐体と、第2の筐体に保持されている透明部材を有する成形品において、透明部材に結露や曇りが生じず、かつ、第1の筐体と第2の筐体の接合部分の外観が良好な成形品、ならびに、前記成形品の製造方法を提供することを目的とする。
<1>第1の筐体と、前記第1の筐体と接合している第2の筐体と、前記第2の筐体に保持されている透明部材を有し、前記第1の筐体および第2の筐体は、それぞれ独立に、ポリアミド樹脂の半結晶化時間が10~60秒であり、かつ、融点が200~280℃であるポリアミド樹脂を含む樹脂組成物から形成され、前記透明部材が鉛筆硬度8H以上、かつ、線膨張係数が1×10-6~9×10-6/℃である成形品;但し、半結晶化時間とは、ポリアミド樹脂の融点+20℃、ポリアミド樹脂の溶融時間5分、結晶化浴温度150℃の条件下において脱偏光光度法により測定した時間をいう。
<2>前記ポリアミド樹脂が、ジアミン由来の構成単位とジカルボン酸由来の構成単位から構成され、前記ジアミン由来の構成単位の50モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸に由来する、<1>に記載の成形品。
<3>前記第1の筐体に含まれるポリアミド樹脂と、前記第2の筐体に含まれるポリアミド樹脂の融点の差が50℃以下である、<1>または<2>に記載の成形品。
<4>前記第1の筐体および第2の筐体は、それぞれ独立に、フィラーを含む、<1>~<3>のいずれか1つに記載の成形品。
<5>前記第1の筐体および第2の筐体の一方は、光吸収性色素を含み、残りの一方には、光透過性色素を含む<1>~<4>のいずれか1つに記載の成形品。
<6>前記透明部材がガラスから構成される、<1>~<5>のいずれか1つに記載の成形品。
<7>カメラ部品である、<1>~<6>のいずれか1つに記載の成形品。
<8>第1の筐体と、第2の筐体を熱溶着することを含み、前記第2の筐体は、透明部材を保持しており、前記第1の筐体および第2の筐体は、それぞれ独立にポリアミド樹脂の半結晶化時間が10~60秒であり、かつ、融点が200~280℃であるポリアミド樹脂を含む樹脂組成物から形成され、前記透明部材が鉛筆硬度8H以上、かつ、線膨張係数が1×10-6~9×10-6/℃である成形品の製造方法;但し、半結晶化時間とは、ポリアミド樹脂の融点+20℃、ポリアミド樹脂の溶融時間5分、結晶化浴温度150℃の条件下において脱偏光光度法により測定した時間をいう。
<9>前記熱溶着がレーザー溶着である、<8>に記載の成形品の製造方法。
<10>前記第1の筐体および第2の筐体の一方は、光吸収性色素を含み、残りの一方には光透過性色素を含む<8>または<9>に記載の成形品の製造方法。
<11>前記第1の筐体に含まれるポリアミド樹脂と、前記第2の筐体に含まれるポリアミド樹脂の融点の差が50℃以下である、<8>~<10>のいずれか1つに記載の成形品の製造方法。
本発明では、結晶化速度が比較的遅いポリアミド樹脂を用いることにより、第1の筐体と第2の筐体の接合の際に、熱溶着をゆっくり進行させることができ、第1の筐体と第2の筐体の界面のギャップが少なくすることができる。このため、第1の筐体と第2の筐体を接合して得られる成形品の内部には、水分などが侵入しにくくなり、透明部材に結露が生じにくくなり、また、曇りにくくなる。加えて、第1の筐体と第2の筐体の界面のギャップが少なくても、接合界面がきれいでないと、外観不良の問題がある。本発明では、第1の筐体と第2の筐体をゆっくり接合させるため、界面がきれいであり、外観に優れた成形品が得られる。
本発明の成形品は、少なくとも、第1の筐体、第2の筐体および透明部材によって形成される、外部から隔てられた中空構造を有することが好ましい。例えば、図1におけるカメラ部品5は、コネクタを保持する樹脂製のケース4(第1の筐体に相当)、樹脂製のレンズホルダ2(第2の筐体に相当)およびレンズ部1(透明部材に相当)によって、コネクタ3を保持する中空構造が形成されている。また、前記中空構造は、必ずしも、第1の筐体、第2の筐体および透明部材のみによって形成される必要はない。本発明の成形品は、第1の筐体、第2の筐体および透明部材に加え、第3の筐体や部材を含めて、外部から隔てられた中空構造が形成されていてもよい。この場合、第3の筐体も、上記所定の結晶化速度および融点を満たすポリアミド樹脂を含む樹脂組成物から形成されることが好ましい。中空構造の密閉度が高いほど、透明部材の曇りや結露を効果的に抑制できる。
本発明において、第1の筐体および第2の筐体は、それぞれ独立に、樹脂組成物から形成される。
第1の筐体の形成に用いられる樹脂組成物と、第2の筐体の形成に用いられる樹脂組成物は、同一であってもよいが、異なっていてもよい。
本発明では、第1の筐体の形成に用いられる樹脂組成物と、第2の筐体の形成に用いられる樹脂組成物は、組成の80質量%以上100質量%未満が共通することが好ましい。特に、前記第1の筐体と第2の筐体の一方を形成する樹脂組成物と他方を形成する樹脂組成物は、ポリアミド樹脂成分の80~100質量%が共通することが好ましい。
尚、レーザー溶着を行う場合、第1の筐体と第2の筐体の一方を形成する樹脂組成物は、光吸収性色素を含むことが好ましい。また、他方の筐体を形成する樹脂組成物は、光透過性色素を含むことがさらに好ましい。
本発明で用いるポリアミド樹脂は、半結晶化時間が10~60秒であり、かつ、融点が200~280℃であるポリアミド樹脂である。前記の範囲とすることにより、溶着の際、軟化している時間が長いため、接合強度が向上する。
半結晶化時間が10秒未満の場合は、樹脂が早く固化してしまい適切な密着強度が得られなくなる。また、半結晶化時間が60秒を超える場合は樹脂が軟らかく、接合の際に適切な圧力を加えることが難しくなる。
ポリアミド樹脂の半結晶化時間の測定は、後述する実施例に記載の方法に従う。実施例に記載の機器等が廃版等により入手不可能な場合、他の同等の性能を有する機器を用いることができる。以下、他の測定方法についても、同様である。
本発明で用いる樹脂組成物は、ポリアミド樹脂を1種類のみ含んでいても、2種類以上含んでいてもよい。本発明で用いる樹脂組成物が、ポリアミド樹脂を2種類以上含む場合、最も配合量の多いポリアミド樹脂の半結晶化時間を本発明におけるポリアミド樹脂の半結晶化時間とする。
本発明では、第1の筐体に含まれるポリアミド樹脂と、第2の筐体に含まれるポリアミド樹脂の、半結晶化時間は、それぞれ独立に、下限値が10秒以上であり、20秒以上であることが好ましく、25秒以上であることがより好ましく、30秒以上であることがさらに好ましい。前記半結晶化時間の上限値は、それぞれ独立に、60秒以下であり、55秒以下が好ましく、50秒以下がより好ましく、45秒以下がさらに好ましい。
このような範囲とすることにより、より第1の筐体と第2の筐体の界面の溶着強度を向上することができる。
ポリアミド樹脂の融点の測定は、後述する実施例に記載の方法に従う。実施例に記載の機器等が廃版等により入手不可能な場合、他の同等の性能を有する機器を用いることができる。
本発明で用いる樹脂組成物が、ポリアミド樹脂を2種類以上含む場合、最も配合量の多いポリアミド樹脂の融点を本発明におけるポリアミド樹脂の融点とする。ポリアミド樹脂が融点を2点以上有する場合、最も低い融点を本発明におけるポリアミド樹脂の融点とする。
本発明では、第1の筐体に含まれるポリアミド樹脂と、第2の筐体に含まれるポリアミド樹脂の、融点の差が50℃以下であることが好ましく、30℃以下であることがより好ましく、20℃以下であることがさらに好ましく、10℃以下であることが一層好ましく、5℃以下であることがより一層好ましい。このような範囲とすることにより、より第1の筐体と第2の筐体の界面のギャップをより少なくすることができる。前記融点の差は0℃が好ましい。
ジアミン成分として、キシリレンジアミン以外のジアミンを用いる場合は、ジアミン由来の構成単位の50モル%未満であり、30モル%以下であることが好ましく、より好ましくは1~25モル%、さらに好ましくは5~20モル%の割合で用いる。
本発明で用いる好ましいポリアミド樹脂としては、メタキシリレンジアミン、アジピン酸およびイソフタル酸から構成されるポリアミド樹脂(MXD6I)、メタキシリレンジアミンおよびアジピン酸から構成されるポリアミド樹脂(MXD6)、メタキシリレンジアミン、パラキシリレンジアミンおよびアジピン酸から構成されるポリアミド樹脂(MP6)、メタキシリレンジアミンおよびセバシン酸から構成されるポリアミド樹脂(MXD10)、メタキシリレンジアミン、パラキシリレンジアミンおよびセバシン酸から構成されるポリアミド樹脂(MP10)が例示される。
数平均分子量(Mn)=2,000,000/([COOH]+[NH2])
ポリアミド樹脂の分子量分布は、例えば、重合時に使用する開始剤や触媒の種類、量および反応温度、圧力、時間等の重合反応条件などを適宜選択することにより調整できる。また、異なる重合条件によって得られた平均分子量の異なる複数種のポリアミド樹脂を混合したり、重合後のポリアミド樹脂を分別沈殿させることにより調整することもできる。
尚、ポリアミド樹脂の吸水率が低くても、水分透過係数が小さいとは言えない。これは、ポリアミド樹脂では、吸水速度と拡散速度が異なるためである。
本発明で用いる樹脂組成物は、上記ポリアミド樹脂と後述するフィラーの合計が全体の90質量%以上を占めることが好ましい。
本発明で用いる樹脂組成物は、上記以外のポリアミド樹脂を1種類または2種類以上含んでいてもよい。このようなポリアミド樹脂としては、ポリアミド4、ポリアミド6、ポリアミド11、ポリアミド12、ポリアミド46、ポリアミド66、ポリアミド610、ポリアミド612、ポリヘキサメチレンテレフタラミド(ポリアミド6T)、ポリヘキサメチレンイソフタラミド(ポリアミド6I)、ポリアミド66/6T、ポリアミド9MT、ポリアミド6I/6T等があげられる。しかしながら、本発明では、これらのポリアミド樹脂は実質的に含まない方が好ましい。実質的に含まないとは、本発明で用いる樹脂組成物において、上記所定の結晶化速度および融点を満たすポリアミド樹脂の含有量の2質量%以下であることをいい、1質量%以下が好ましく、0.1質量%以下がより好ましい。
本発明で用いる樹脂組成物は、フィラーを含んでいてもよい。フィラーは有機フィラーであっても、無機フィラーであってもよいが、無機フィラーが好ましい。
無機フィラーは、ガラスフィラー、炭素繊維、シリカ、アルミナおよびレーザーを吸収する材料をコートした無機粉末等のレーザー光を吸収しうるフィラーが例示され、ガラスフィラーが好ましく、ガラス繊維がより好ましい。
ガラス繊維の形態は、単繊維や複数本撚り合わせたものを連続的に巻き取った「ガラスロービング」、長さ1~10mmに切りそろえた「チョップドストランド」、長さ10~500μm程度に粉砕した「ミルドファイバー」などのいずれであってもよい。かかるガラス繊維としては、旭ファイバーグラス社より、「グラスロンチョップドストランド」や「グラスロンミルドファイバー」の商品名で市販されており、容易に入手可能である。
本発明で用いるガラス繊維は、集束剤で集束されていてもよい。この場合の集束剤としては、酸系集束剤が好ましい。
本発明で用いる樹脂組成物は、フィラーを1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、合計量が上記範囲となることが好ましい。
本発明で用いる樹脂組成物は、一方が光吸収性色素を含むことが好ましい。このような構成とすることにより、レーザー溶着が可能になる。本発明で用いる樹脂組成物の他方は、光透過性色素を含んでいてもよい。光透過性色素を含むことにより、第1の筐体と第2の筐体をより強固にレーザー溶着することができる。
光吸収性色素の配合量は、配合する場合、樹脂組成物に含まれる樹脂成分100質量部に対し0.01~1質量部であることが好ましい。
市販品としては、オリエント化学工業社製の着色剤であるe-BIND LTW-8731H、e-BIND LTW-8701H等が例示される。また、有彩色色素を2種類以上混ぜて黒系色素としたものを用いてもよい。
光透過性色素の含有量は、配合する場合、樹脂組成物の0.001質量%以上であることが好ましく、0.006質量%以上であることがより好ましく、さらには、0.018質量%以上、0.024質量%以上、0.030質量%以上、0.050質量%以上であってもよい。上限値としては、5.0質量%以下であることが好ましく、2.0質量%以下であることがより好ましく、1.0質量%以下であることがさらに好ましく、0.2質量%以下、0.1質量%以下、0.06質量%以下であってもよい。光透過性色素は、1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、合計量が上記範囲となることが好ましい。
本発明で用いる樹脂組成物は、ポリアミド樹脂以外の他の樹脂成分を1種類または2種類以上含んでいてもよい。他の樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリカーボネート樹脂、ポリアセタール樹脂等の熱可塑性樹脂を用いることができる。
本発明で用いる樹脂組成物は、ポリアミド樹脂以外の樹脂成分を実質的に配合しない構成としてもよく、例えば、樹脂組成物に含まれる樹脂成分全量の5質量%以下、さらには、1質量%以下、特には、0.4質量%以下とすることもできる。
本発明で用いる樹脂組成物はタルクを含んでいてもよい。本発明では、タルクを配合することにより、結晶化を促進することができる。
本発明で用いる樹脂組成物における、タルクの配合量は、樹脂組成物に対し、0.05~20質量%であることが好ましく、0.1~10質量%であることがより好ましく、0.15~5質量%であることがさらに好ましく、0.2~1.0質量%であることが一層好ましい。タルクは、1種類のみを用いてもよいし、2種類以上を併用してもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。
本発明で用いる樹脂組成物は、離型剤を含んでいてもよい。離型剤としては、例えば、脂肪族カルボン酸、脂肪族カルボン酸の塩、脂肪族カルボン酸とアルコールとのエステル、数平均分子量200~15,000の脂肪族炭化水素化合物、ポリシロキサン系シリコーンオイルなどが挙げられる。
これらの中では、パラフィンワックス、ポリエチレンワックスまたはポリエチレンワックスの部分酸化物が好ましく、パラフィンワックス、ポリエチレンワックスがより好ましい。
本発明の成形品は、鉛筆硬度8H以上、かつ、線膨張係数が1×10-6~9×10-6/℃である透明部材を含む。このような透明部材は、例えば、カメラ部品のレンズ部を構成する。
透明部材の鉛筆硬度は、8H~9Hが好ましい。鉛筆硬度は、JIS K 5600に従って測定された値である。
透明部材の線膨張係数は、5×10-6~9×10-6/℃が好ましい。線膨張係数はJIS K 7197に従って測定された値である。
透明部材の材質としては、ガラスや樹脂が例示され、ガラスが好ましい。
本発明における透明部材は、第2の筐体に保持されている。保持されている例としては、透明部材が第2の筐体に直接または間接的に嵌合している状態が挙げられる。間接的に嵌合しているとは、パッキン等の部材を介して嵌合している状態をいう。
本発明の成形品の製造方法は、第1の筐体と、第2の筐体を溶着することを含み、前記第2の筐体は、透明部材を保持する第1の筐体と、第2の筐体を熱溶着することを含み、前記第2の筐体は、透明部材を保持しており、前記第1の筐体および第2の筐体は、それぞれ独立にポリアミド樹脂の半結晶化時間が10~60秒であり、かつ、融点が200~280℃であるポリアミド樹脂を含む樹脂組成物から形成され、融点の差が50℃以下であり、前記透明部材が鉛筆硬度8H以上、かつ、線膨張係数が1×10-6~9×10-6/℃であることを含む。半結晶化時間とは、ポリアミド樹脂の融点+20℃、ポリアミド樹脂の溶融時間5分、結晶化浴温度150℃の条件下において脱偏光光度法により測定した時間をいう。
熱溶着の温度は、ポリアミド樹脂の融点を基準に定められ、ポリアミド樹脂の融点+50~300℃に加熱されることが好ましい。ここでのポリアミド樹脂の融点は、第1の筐体および第2の筐体に含まれる、所定の結晶化速度および融点を満たすポリアミド樹脂のうち、最も融点の低いポリアミド樹脂を基準に設定される。
次に、レーザー溶着方法について説明する。本発明では、第1の筐体と第2の筐体をレーザー溶着させて成形品とすることができる。この場合、第1の筐体と第2の筐体の一方は、透過樹脂部材であり、他方は吸収樹脂部材となる。レーザー溶着することによって透過樹脂部材と吸収樹脂部材を、接着剤を用いずに、強固に溶着することができる。
第1の筐体と第2の筐体の接合部位の形状は特に制限されないが、部材同士をレーザー溶着により接合して用いるため、通常、少なくとも面接触箇所(平面、曲面)を有する形状である。レーザー溶着では、透過樹脂部材を透過したレーザー光が、吸収樹脂部材に吸収されて、溶融し、両部材が溶着される。本発明では、第1の筐体および第2の筐体がゆっくり接合するため、良好な接合を達成することができる。ここで、レーザー光が透過する部材の厚み(レーザー光が透過する部分におけるレーザー透過方向の厚み)は、用途、樹脂組成物の組成その他を勘案して、適宜定めることができるが、例えば5mm以下であり、好ましくは4mm以下である。
このようにして透過樹脂部材と吸収樹脂部材を溶着された成形品は、高い接合強度を有する。
(ポリアミド(MXD6)の合成)
特開2011-140620号公報の段落0038の記載に従って、ポリアミド樹脂を得た。得られたポリアミド樹脂を、「MXD6」という。
攪拌機、分縮器、全縮器、温度計、滴下ロートおよび窒素導入管、ストランドダイを備えた反応容器に、精秤したセバシン酸12,135g(60mol)、次亜リン酸ナトリウム一水和物(NaH2PO2・H2O)3.105g(ポリアミド樹脂中のリン原子濃度として50質量ppm)、酢酸ナトリウム1.61gを入れ、十分に窒素置換した後、さらに少量の窒素気流下で系内を攪拌しながら170℃まで加熱した。酢酸ナトリウム/次亜リン酸ナトリウム一水和物のモル比は、0.67とした。
これにメタキシリレンジアミンとパラキシリレンジアミンの7:3の混合ジアミン8,172g(60mol)を攪拌下に滴下し、生成する縮合水を系内へ除きながら系内を連続的に昇温した。混合メタキシリレンジアミンの滴下終了後、内温を260℃として40分間溶融重合反応を連続した。
その後、系内を窒素で加圧し、ストランドダイからポリマーを取り出して、これをペレット化し、約18kgのポリアミド樹脂を得た。得られたポリアミドの融点は215℃、ガラス転移点は、64.4℃、数平均分子量は14,286、相対粘度(96%硫酸中、樹脂濃度1g/100cc、温度25℃で測定)は2.09、末端アミノ基濃度は60.0μ当量/g、末端カルボキシル基濃度は80.0μ当量/gであった。
特開2010-286544号公報の段落0052の記載に従い、テレフタル酸と1,9-ノナンジアミンを主成分とする、ポリアミド樹脂を合成した。得られたポリアミド樹脂を、「9T」という。
100mm×100mm×1mm厚のキャビティを持った金型を用いて日精樹脂工業社製、NEX80III-9Eを用いてシリンダ温度280℃、金型表面温度135℃で成形した。次に、図2に示すように、内径67mm、内部の高さ80mmのアルミ製の円筒状のカップ11の内部に25gの塩化カルシウム粒子12を入れた。カップの内部底面から50mmの位置において、上記1mmの厚みのフィルム13を用いて封止し、40℃、相対湿度90%の雰囲気下に40時間静置した。塩化カルシウム粒子の質量を計測し、静置前との差分(増加分)を透過した水分量とし、水分透過係数を算出した。
水分透過係数の単位は、g・mm/day・m2である。
半結晶化時間とは、ポリアミド樹脂の融点+20℃、ポリアミド樹脂の溶融時間5分、結晶化浴温度150℃の条件下において脱偏光光度法により測定した。半結晶化時間測定装置は、(株)コタキ製作所製、型式:MK701を用いた。
具体的には、ポリアミド樹脂を、単軸押出機等を用いて融点+20℃にて溶融しガラス転移温度-5℃のチルロール温度にて100μmの厚さに成形したフィルムを5枚重ねたものをポリアミド樹脂の融点+20℃の熱風環境で3分間溶融した後、150℃のオイルバスにて結晶化させたときの結晶化が1/2進行するまでの時間を、上記脱偏光光度法により測定した。
半結晶化時間の単位は、秒である。
融点は、DSC(示差走査熱量測定)法により観測される昇温時の吸熱ピークのピークトップの温度として測定した。
測定には、DSC測定器を用い、試料量は約1mgとし、雰囲気ガスとしては窒素を30mL/分で流し、昇温速度は10℃/分の条件で室温から予想される融点以上の温度まで加熱し溶融させた際に観測される吸熱ピークのピークトップの温度から融点を求めた。
DSC測定器としては、島津製作所(SHIMADZU CORPORATION)社製、DSC-60を用いた。
融点の単位は、℃である。
T756H:ガラス繊維、日本電気ガラス社製、ECS03T-756H(商品名)、重量平均繊維径10.5μm、カット長3~4mm、
<光透過性色素>
8731H:オリエント化学工業社製、e-BIND LTW-8731H(商品名)、ポリアミド66と光透過性色素のマスターバッチ
<光吸収性色素>
カーボンブラック(三菱化学社製、MA600B)
<タルク>
ミクロンホワイト#5000S:林化成社製
<離型剤>
ライトアマイドWH255:共栄社化学社製
<光透過性筐体の作製>
<<樹脂組成物の製造>>
表2に示すポリアミド樹脂とタルクと離型剤と光透過性色素をそれぞれ秤量し、ドライブレンドした後、二軸押出機(東芝機械社製、TEM26SS)のスクリュー根元から2軸スクリュー式カセットウェイングフィーダ(クボタ社製、CE-W-1-MP)を用いて投入した。また、表2に示すガラス繊維については振動式カセットウェイングフィーダ(クボタ社製、CE-V-1B-MP)を用いて押出機のサイドから上述の二軸押出機に投入し、樹脂成分等と溶融混練し、ペレットを得た。押出機の温度設定は280℃とした。
上記で得られたペレットを射出成形機(住友重機械工業社製、SE50D)でシリンダ温度280℃、金型表面温度110℃で成形した。
<<樹脂組成物の製造>>
表3に示すポリアミド樹脂とタルクと離型剤と光吸収性色素をそれぞれ秤量し、ドライブレンドした後、二軸押出機(東芝機械社製、TEM26SS)のスクリュー根元から2軸スクリュー式カセットウェイングフィーダ(クボタ社製、CE-W-1-MP)を用いて投入した。表3に示す光吸収性色素については、表3に示す分量の範囲内のポリアミド樹脂の一部を用いてマスターバッチ化してから投入した。また、表3に示すガラス繊維については振動式カセットウェイングフィーダ(クボタ社製、CE-V-1B-MP)を用いて押出機のサイドから上述の二軸押出機に投入し、樹脂成分等と溶融混練し、ペレットを得た。押出機の温度設定は、280℃とした。
上記で得られたペレットを射出成形機(住友重機械工業社製、SE50D)でシリンダ温度280℃、金型表面温度110℃で成形した。
上記で得られた光透過性筐体に透明部材としてガラスレンズを嵌め込み、光吸収性筐体とレーザー溶着した。光透過性筐体と光吸収性筐体を重ね、光透過性筐体側からレーザー照射した。ガラスレンズは、鉛筆硬度が8Hであり、線膨張係数が約8.5×10-6である。レーザー光波長は940nm(半導体レーザー)、溶着スポット径は2.0mm、溶着長さは20mmでレーザーを照射した。レーザー光のスキャン速度は5mm/秒、レーザー出力は13W、クランプ圧力は0.5MPaとした。
レーザー溶着装置は、スキャンタイプのパーカーコーポレーション社製、PARK LASER SYSTEMを用いた。
得られた成形品を、40℃、相対湿度90%の環境下に40時間静置した後、曇りおよび結露を目視にて評価した。
A:結露および曇りが認められなかった。
B:結露および曇りの少なくとも一方が認められた。
得られた成形品の光吸収性筐体と光透過性筐体の界面を目視で確認した。
A:界面がきれいであった。
B:上記A以外であった。
実施例1において、光吸収性筐体と光透過性筐体に用いるポリアミド樹脂をそれぞれ下記表4に示すポリアミド樹脂に変更し、他は同様に行った。
<光吸収性筐体の作製>
<<樹脂組成物の製造>>
表3に示すポリアミド樹脂とタルクと離型剤と光吸収性色素をそれぞれ秤量し、ドライブレンドした後、二軸押出機(東芝機械社製、TEM26SS)のスクリュー根元から2軸スクリュー式カセットウェイングフィーダ(クボタ社製、CE-W-1-MP)を用いて投入した。表3に示す光吸収性色素については、表3に示す分量の範囲内のポリアミド樹脂の一部を用いてマスターバッチ化してから投入した。また、表3に示すガラス繊維については振動式カセットウェイングフィーダ(クボタ社製、CE-V-1B-MP)を用いて押出機のサイドから上述の二軸押出機に投入し、樹脂成分等と溶融混練し、ペレットを得た。押出機の温度設定は、280℃とした。
上記で得られたペレットを射出成形機(住友重機械工業社製、SE50D)でシリンダ温度280℃、金型表面温度110℃で成形した。
<<樹脂組成物の製造>>
表2に示すポリアミド樹脂とタルクと離型剤と光透過性色素をそれぞれ秤量し、ドライブレンドした後、二軸押出機(東芝機械社製、TEM26SS)のスクリュー根元から2軸スクリュー式カセットウェイングフィーダ(クボタ社製、CE-W-1-MP)を用いて投入した。また、表2に示すガラス繊維については振動式カセットウェイングフィーダ(クボタ社製、CE-V-1B-MP)を用いて押出機のサイドから上述の二軸押出機に投入し、樹脂成分等と溶融混練し、ペレットを得た。押出機の温度設定は、280℃とした。
上記で得られたペレットを射出成形機(住友重機械工業社製、SE50D)でシリンダ温度280℃、金型表面温度110℃で成形した。
上記で得られた光吸収性筐体に透明部材としてガラスレンズを嵌め込み、光透過性筐体とレーザー溶着した。光吸収性筐体と光透過性筐体を重ね、光透過性筐体側からレーザー照射した。ガラスレンズは、鉛筆硬度が8Hであり、線膨張係数が約8.5×10-6である。レーザー光波長は940nm(半導体レーザー)、溶着スポット径は2.0mm、溶着長さは20mmでレーザーを照射した。レーザー光のスキャン速度は5mm/秒、レーザー出力は13W、クランプ圧力は0.5MPaとした。
レーザー溶着装置は、スキャンタイプのパーカーコーポレーション社製、PARK LASER SYSTEMを用いた。
実施例3において、光吸収性筐体と光透過性筐体に用いるポリアミド樹脂をそれぞれ表4に示すポリアミド樹脂に変更し、他は同様に行った。
2 樹脂製のレンズホルダ
3 コネクタ
4 コネクタを保持する樹脂製のケース
5 カメラ部品
11 カップ
12 塩化カルシウム粒子
13 1mmの厚みのフィルム
Claims (11)
- 第1の筐体と、前記第1の筐体と接合している第2の筐体と、前記第2の筐体に保持されている透明部材を有し、前記第1の筐体および第2の筐体は、それぞれ独立に、ポリアミド樹脂の半結晶化時間が10~60秒であり、かつ、融点が200~280℃であるポリアミド樹脂を含む樹脂組成物から形成され、前記透明部材が鉛筆硬度8H以上、かつ、線膨張係数が1×10-6~9×10-6/℃である成形品;但し、半結晶化時間とは、ポリアミド樹脂の融点+20℃、ポリアミド樹脂の溶融時間5分、結晶化浴温度150℃の条件下において脱偏光光度法により測定した時間をいう。
- 前記ポリアミド樹脂が、ジアミン由来の構成単位とジカルボン酸由来の構成単位から構成され、前記ジアミン由来の構成単位の50モル%以上がキシリレンジアミンに由来し、前記ジカルボン酸由来の構成単位の70モル%以上が炭素数4~20のα,ω-直鎖脂肪族ジカルボン酸に由来する、請求項1に記載の成形品。
- 前記第1の筐体に含まれるポリアミド樹脂と、前記第2の筐体に含まれるポリアミド樹脂の融点の差が50℃以下である、請求項1または2に記載の成形品。
- 前記第1の筐体および第2の筐体は、それぞれ独立に、フィラーを含む、請求項1~3のいずれか1項に記載の成形品。
- 前記第1の筐体および第2の筐体の一方は、光吸収性色素を含み、残りの一方には、光透過性色素を含む請求項1~4のいずれか1項に記載の成形品。
- 前記透明部材がガラスから構成される、請求項1~5のいずれか1項に記載の成形品。
- カメラ部品である、請求項1~6のいずれか1項に記載の成形品。
- 第1の筐体と、第2の筐体を熱溶着することを含み、
前記第2の筐体は、透明部材を保持しており、
前記第1の筐体および第2の筐体は、それぞれ独立にポリアミド樹脂の半結晶化時間が10~50秒であり、かつ、融点が200~280℃であるポリアミド樹脂を含む樹脂組成物から形成され、前記透明部材が鉛筆硬度8H以上、かつ、線膨張係数が1×10-6~9×10-6/℃である成形品の製造方法;但し、半結晶化時間とは、ポリアミド樹脂の融点+20℃、ポリアミド樹脂の溶融時間5分、結晶化浴温度150℃の条件下において脱偏光光度法により測定した時間をいう。 - 前記熱溶着がレーザー溶着である、請求項8に記載の成形品の製造方法。
- 前記第1の筐体および第2の筐体の一方は、光吸収性色素を含み、残りの一方には光透過性色素を含む請求項8または9に記載の成形品の製造方法。
- 前記第1の筐体に含まれるポリアミド樹脂と、前記第2の筐体に含まれるポリアミド樹脂の融点の差が50℃以下である、請求項8~10のいずれか1項に記載の成形品の製造方法。
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KR20210156881A (ko) | 2021-12-27 |
CN113608314B (zh) | 2023-09-15 |
JPWO2018123171A1 (ja) | 2019-10-31 |
KR20190099446A (ko) | 2019-08-27 |
EP3564723A1 (en) | 2019-11-06 |
EP3564723B1 (en) | 2024-03-27 |
KR102546859B1 (ko) | 2023-06-22 |
JP6998889B2 (ja) | 2022-02-10 |
EP3564723A4 (en) | 2020-09-30 |
CN110140075A (zh) | 2019-08-16 |
CN113608314A (zh) | 2021-11-05 |
CN110140075B (zh) | 2024-03-22 |
KR102546858B1 (ko) | 2023-06-22 |
US20190331984A1 (en) | 2019-10-31 |
US11397372B2 (en) | 2022-07-26 |
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