JP2014128900A - Polyurethane resin integrally-molded metal heat insulation long material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic resin filled metal-made long material which is used majorly in window frame building materials and molded integrally with a polyurethane resin and does not undergo shrinkage of the polyurethane resin after integral molding without use of a primer on the metal side, filling with an inorganic filler or after repetition of high temperature/low temperature thermal hysteresis.SOLUTION: A metal long material comprises a metal-made long tub-like frame filled with a polyurethane resin, and the polyurethane resin layer includes a solid long linear product along the longitudinal direction of the polyurethane resin layer. The metal long material is produced by a method of producing the metal long material, the method comprising: arranging the solid linear product along the central vicinity, in the longitudinal direction, of the metal long material; pouring a polyurethane resin molding composition at a time; and hardening for integral molding, in a step of injecting the polyurethane resin molding composition in a metal-made long tub-like frame.

Description

The present invention relates to a long metal material having heat insulation used for a window frame or the like, and more particularly to a long metal material integrally formed.

Conventionally, a heat insulating sash by integrally molding a long metal material and a polyurethane resin used as a heat insulating material is known. However, the adhesion of polyurethane long resin (such as electrodeposited aluminum mold) and polyurethane resin is poor, the molded polyurethane resin is self-shrinking, and aluminum metal and polyurethane resin Since the linear expansion coefficients are greatly different, separation may occur between the long metal material and the polyurethane resin after integral molding, and as a result, a space portion may occur. As a result, when used as a window frame, not only does the heat insulation performance deteriorate due to the displacement, but also the problem that rainwater enters from the displacement, and as a result, mold, etc. occurs, as a heat insulation sash for the window frame. It is not satisfactory.

As a countermeasure, a method has been proposed in which a primer is applied to the electrodeposited surface of an aluminum mold material to improve the adhesion between the mold material and the polyurethane resin (Patent Document 1: Japanese Patent Application Laid-Open No. 2007-045976). However, this method makes it difficult to apply a primer effectively and uniformly to a window frame material having a complicated shape, and as a result, the thermal insulation sash is repeatedly placed under cold or high temperature for a long time, and shrinks and expands. If the effect of the primer is not sufficient when it is repeated, the long metal material and the polyurethane resin may peel off, and a gap (hereinafter referred to as “deviation”) due to peeling may occur.

Further, a method has been proposed in which a fibrous inorganic filler is mixed with polyurethane resin to reduce the shrinkage (Patent Document 2: Japanese Patent Application Laid-Open No. 2007-332212). However, in this method, the viscosity of the polyurethane raw material is considerably increased, and a special molding machine is required to cope with the inorganic filler, which causes problems in equipment and cost.

Patent Document 3 (Japanese Patent Application Laid-Open No. 2007-291617) discloses a method in which a polyurethane resin raw material is injected in two portions and glass roving is put in the vicinity of the center of the resin so as to be integrally formed. However, with this method, the complexity of the process in which the raw material must be injected in two steps, and relatively large bubbles are generated from the glass roving and remain in the molding resin. There was a case.

JP2007-045976 JP2007-332212 JP2007-291617

The present invention is a long metal material integrally molded with a polyurethane resin, which is mainly used for window frame building materials, and it is polyurethane after integral molding without using a primer on the metal side or filling with an inorganic filler. It is an object of the present invention to provide a synthetic resin-filled metal long shape material that does not shrink and does not change in shrinkage even when repeated high-temperature and low-temperature thermal history is repeated.

As a result of repeated studies to solve such problems, a metal long shape material filled with polyurethane resin and a manufacturing method thereof have been completed.
The present invention relates to a long metal material in which a polyurethane long resin frame is filled with a polyurethane resin, and the polyurethane resin layer encloses a solid long linear object along the longitudinal direction of the polyurethane resin layer. Providing long metal materials.
In the process of injecting the polyurethane resin-forming composition into a long metal frame made of metal, the present invention arranges a solid linear material along the vicinity of the center in the longitudinal direction of the long metal material, and then polyurethane. The present invention also provides a method for producing a long metal material, in which a resin-forming composition is poured at once and cured and integrally formed.

The heat-insulating sash obtained in this way is less susceptible to shrinkage after molding or due to changes in ambient temperature because the shrinkage change of the resin part is suppressed, and when used as a heat-insulating sash for window frames, Deviation from the urethane resin does not occur and the original performance can be exhibited.

The perspective view of the synthetic resin filling type | mold metal long shape material of this invention is shown. It is sectional drawing which shows the manufacturing method of the synthetic resin filling type | mold metal long shape material of this invention.

Hereinafter, the present invention will be described with reference to embodiments shown in the drawings, but the present invention is not limited to the embodiments shown in the drawings.
FIG. 1 shows a perspective view of a synthetic resin-filled long metal material of the present invention. Moreover, the structure inside the frame of a metal long shape material is also shown.

As shown in FIG. 1, in the long metal material, a non-foaming polyurethane resin 3 is filled in a metal bowl-like frame material 1. Furthermore, a solid long linear object 2 is embedded in the polyurethane resin 3 in the frame along the longitudinal direction of the frame member 1. Thus, the shrinkage | contraction of the polyurethane resin 3 is suppressed because the solid elongate linear object 2 is included along the longitudinal direction of the polyurethane resin 3. FIG.

FIG. 2 is a cross-sectional view illustrating a method for producing a synthetic resin-filled long metal material of the present invention.
FIG. 2A shows a cross section of the frame member 1 before starting the step (1).
B of FIG. 2 shows the state (cross section) which has arrange | positioned the solid elongate linear object 2 to the frame material 1 in a process (1). In FIG. 2B, one solid long linear object 2 is shown. However, the number of the solid long linear object 2 may be plural, and 0.3 to 10 per 1 cm ² of the cross section of the space of the frame member 1 in which the solid long linear object 2 and the polyurethane resin 3 are arranged. For example, it may be 1-3.
FIG. 2C shows a state (cross section) in which the urethane resin is cured around the solid long linear object 2 in the frame member 1 by the step (2).
FIG. 2D is a diagram illustrating a state in which a part of the bottom surface of the frame member 1 is cut out after the step (2). By cutting out a part of the bottom surface of the frame material to expose the polyurethane resin, the long material exhibits good heat insulation performance.

The polyurethane resin preferably has a hardness equal to or higher than a predetermined value so that when the long metal material is used as a building material such as a window frame, a suitable rigidity can be imparted to the building material. In the present invention, the polyurethane resin is non-foaming and preferably has a density of 1.05 to 1.18 g / cm ³ . Further, in the measuring method JIS K 6911, it is preferable that the bending strength is 60 to 90 MPa, the bending modulus is 1000 to 2000 MPa, and the tensile strength is 35 to 60 MPa. The Shore D hardness is preferably 60 or more.

In general, the metal long frame-like frame is preferably made of aluminum, but may be made of other metals such as iron and stainless steel.

The solid long linear object is preferably a linear object having a maximum cross-sectional dimension of 0.1 to 2 mm, preferably 0.2 to 1.5 mm. The cross section of the solid long linear object may be circular or angular as long as it does not have a factor for generating bubbles. The cross-sectional shape may be, for example, a circle, an ellipse, or a polygon including a triangle and a rectangle. When the cross-sectional shape is circular, the maximum cross-sectional dimension is the diameter (or diameter). The solid long linear material is preferably an inorganic material having a linear expansion coefficient of 0.5 to 30 × 10 ⁻⁶ / K. It is important that the solid long linear object does not have a factor that generates bubbles at the time of integral molding. For this purpose, it is preferable that there is no space on the surface or inside of the solid long linear object. The diameter of the solid long linear material is also important. When the diameter is 2 mm or more, it becomes easy to entrain air when integrally molded with the polyurethane resin raw material to be injected (need to show viscosity), and in the cured resin Air bubbles may remain in the surface, which is not preferable.

As the inorganic substance constituting the solid long linear object, metal (for example, iron, stainless steel, aluminum, copper, bronze, brass, nickel) or glass is preferable.
As the solid long linear object, for example, an iron wire or a glass wire having a diameter of 0.1 to 1.5 mm can be used.
It is preferable to use a solid long linear material in a weight ratio of 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyurethane resin. When the amount of the solid long linear material is 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyurethane resin, the heat insulation performance is not lowered, or air entrainment does not occur at the time of integral molding, The solid long linear material can satisfactorily suppress the shrinkage of the polyurethane resin.

The polyurethane resin to be filled is preferably a two-component reaction system composed of a polyol component having a hydroxyl group and an isocyanate component. Furthermore, it is preferable that it is a polyurethane resin with various performance, for example, heat insulation and resin strength (hardness).

The polyurethane resin is a polyol component using a general polyether polyol alone or in combination, a crosslinking agent, a catalyst, and a main agent containing a foam stabilizer as necessary, and an isocyanate component (organic polyisocyanate compound) as a curing agent. In addition, a mixture of two liquids of a main agent and a curing agent may be used for reaction curing at room temperature.

The polyol component may consist solely of polyether polyol, or may comprise a mixture of polyether polyol and other polyols, such as a mixture of polyether polyol and polyester polyol. The amount of other polyols may be up to 50% by weight, for example 40-0.5% by weight, based on the polyol component.
Polyether polyols include hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and sucrose, compounds containing amino groups and hydroxyl groups such as diethanolamine and triethanolamine, or ethylenediamine. Polyether having 2 to 8 hydroxyl groups in the molecule to which an alkylene oxide such as ethylene oxide or propylene oxide has been added, and an average hydroxyl group equivalent of 100 to 5000, using an amino group-containing compound such as diethylenetriamine or diaminotoluene as an initiator A polyol or the like is used.
In addition, a polymer polyol obtained by grafting a polyvinyl filler based on the above-described polyether polyol and a PHD polyol in which a polyurea component is dispersed can also be used.
In order to obtain the resin physical properties for the purpose of the present invention, it is particularly preferable to use a polyether polyol having an average functionality of 2.5 to 4.0. For this, one kind of polyether polyol may be used, or a plurality of polyether polyols may be mixed and used.
The viscosity of the polyol is preferably 100 to 10,000 mPa · s, particularly 300 to 5000 mPa · s at 25 ° C.

Examples of organic polyisocyanate compounds that are curing agents include 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), polymethylene polyphenyl polyisocyanate ( (Polymeric MDI) or those obtained by urethane modification or carbodiimide modification thereof alone or in combination are preferably used.

As the crosslinking agent, an initiator of polyether polyol or the like can be used. In addition, polyether polyols having an average hydroxyl equivalent weight of 100 or less obtained by adding alkylene oxide to these may also be used as a crosslinking agent. Aromatic amine compounds such as diethyltoluenediamine can also be used. The amount of the crosslinking agent is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyol component.

As the catalyst, an amine catalyst or a metal catalyst is used alone or in combination.
Examples of amine catalysts include triethylenediamine, pentamethyldiethylenetriamine, 1,8-diazabicyclo-5,4,0-undecene-7, dimethylaminoethanol, tetramethylethylenediamine, dimethylbenzylamine, tetramethylhexamethylenediamine, bis ( Tertiary amines such as 2-dimethylaminoethyl) ether, N, N′-dimethylaminopropylamine, N, N′-dimethylethanolamine, 1-isobutyl-2-methylimidazole are used.

Examples of the metal catalyst include organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate and tin octoate, and metal compounds such as potassium acetate.
The amount of the catalyst is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the polyol component.

Examples of foam stabilizers that can be used as needed include silicone foam stabilizers, which are preferably used to stably refine the foam produced by the air mixed when mixing the two liquids of the main agent and the curing agent. . The amount of the foam stabilizer is preferably 0.01 to 3 weights with respect to 100 parts by weight of the polyol component.

The main agent may contain other additives (for example, a colorant, an ultraviolet absorber, and an antioxidant). The amount of the other additive is preferably 5 parts by weight or less, for example, 0.1 to 3 parts by weight with respect to 100 parts by weight of the polyol component.
When mixing two liquids of the main agent and curing agent and reaction curing at room temperature, isocyanate group / hydroxyl group = 0.7 to 1.4 (equivalent ratio, NCO index), especially in the range of 0.8 to 1.2. It is preferable to select the amounts of the main agent and the curing agent so as to cause reaction curing.
About the water | moisture content in a main ingredient, the water | moisture content mixed at the time of mix | blending the water | moisture content initially contained in these, such as a polyol, a crosslinking agent, a catalyst, and a foam stabilizer (generally 0.2 weight% or less with respect to a main ingredient, for example, Except for 0.005 to 0.15% by weight, it is preferable not to add intentionally.

The polyurethane resin is preferably non-foamed (does not foam by intentionally adding water to the main agent). Considering the moisture contained from the beginning of each raw material used for the main agent or the moisture mixed when blending these, 1.0 g / cm ³ or more, for example, 1.02 to 1.25 g / cm ³ , particularly 1.05 to A density of 1.18 g / cm ³ is preferred.
When the polyurethane resin is non-foamed, the strength of the polyurethane resin for maintaining the shape of the electrodeposited aluminum mold can be easily obtained, and deformation of the heat-insulating sash that is used can be prevented.
The reactivity of the two-component reaction curable polyurethane resin (main agent and curing agent) is preferably 10 to 100 seconds in gel time when the raw material temperature is 25 ° C. Particularly preferred is 15 to 60 seconds. More preferred is 20 to 50 seconds. The gel time refers to the time for reaction hardening to start and the resin to gel after mixing of the main agent and the curing agent.

The method for producing the long metal material of the present invention is as follows.
(1) a step of setting a solid long linear object on a metal long bowl-shaped frame;
(2) Thereafter, the process includes pouring the polyurethane resin-forming composition into a long bowl-shaped frame at a time, curing the polyurethane resin-forming composition, and integrally molding them.

Process (1)
A solid long linear object is set in the center of the cross section in the longitudinal direction of the metal long bowl-shaped frame. Supports solid long straight objects as needed. Both ends of the long bowl-shaped frame are sealed with tape or foam so that the resin raw material liquid does not leak.

Process (2)
A polyurethane resin is poured into a long metal frame at once (in a short time). That is, after mixing the polyol component and the isocyanate component, the mixture is poured into a long bowl-shaped frame. A method of pouring continuously along the long bowl-like frame is preferable. (If the reaction of the raw material is too fast, the resin will not be uniformly dispersed. If the reaction is too slow, the productivity will be lowered, and it will be important to adjust the reactivity as described above.)

The resin is then cured. The polyol component and the isocyanate component react to cure the polyurethane resin to form a cured polyurethane resin that is preferably non-foamed.
The reaction start time at 25 ° C. (the time from the mixing of the polyol component and the isocyanate component to the start of the reaction (exotherm)) is preferably 1 to 60 seconds, particularly 2 to 20 seconds.
The long metal material molded integrally with the polyurethane resin is manufactured as described above. However, since heat is conducted through the metal frame as it is, when using it as a heat insulating sash, A part of the bottom surface of the frame is cut away to expose the polyurethane resin (see FIG. 2D), so that the heat insulating performance is exhibited.

Hereinafter, although the metal long shape material of this invention is demonstrated more concretely using an Example, this invention is not limited to the Example mentioned later. In Examples, “parts” means “parts by weight” and “%” means “% by weight” unless otherwise specified.

[Preparation of each material]
Aluminum channel :
An AC12141 manufactured by Kogyo Co., Ltd. cut to a length of 500 mm was prepared.
12 (outside dimension height) x 14 (outside dimension width) x 500 (length) mm, aluminum thickness 1 mm
Inner volume 1.1x1.3x50cm = 71.5cm ³

As pretreatment of the aluminum channel, absorbent cotton soaked with acetone was used to wipe off oil adhering to the inside of the aluminum channel.
When measuring the molding shrinkage rate (%), which will be described later, in order to eliminate the factors that cause the aluminum channel and polyurethane resin to adhere and reduce molding shrinkage, a release agent is applied inside the aluminum channel, The polyurethane resin was prevented from adhering.

Solid long straight line:
Iron wire (use one)
1. Piano wire manufactured by Tsuchino Co., Ltd.Weight 0.018 g / cm Diameter 0.52 to 0.55 mm
2. UNIQLO WIRE manufactured by Tsuchino Co., Ltd. Weight 0.088g / cm Diameter 1.1 ~ 1.2mm
Aluminum wire (use one)
1. Daiso Aluminum Wire Weight 0.185g / cm Diameter 3mm
Glass rod (use one)
1. Pyrex (registered trademark) glass rod manufactured by Fuji Rika Kogyo Co., Ltd. Weight 0.074g / cm Diameter 2mm
Roving glass (for comparison)
ERS1150-811 manufactured by Central Glass Co., Ltd.Weight 0.0115g / cm
(Wound about 10 strands of about 200-300 glass fibers with a diameter of 10-24μm)

Blending raw materials for polyurethane resin The following two-component reaction-curable polyurethane resin was used.
(1) Main agent
100 parts of polyoxypropylene triol (3f, MW 450) [Sumiphen TM manufactured by Sumika Bayer Urethane Co., Ltd.]
Triethylenediamine 33% dipropylene glycol solution 2.0 parts Dibutyltin dilaurate 0.1 part (2) Curing agent Polymethylene polyphenyl polyisocyanate [Sumika Bayer Urethane Co., Ltd., Sumidur 44V20]
(3) Mixing ratio of main agent and hardener Main agent / hardener = 53/47 parts (NCO Index 100)
Raw material temperature 40 ℃ each
Discharge rate (main agent + curing agent) 19.1g / sec
(4) Reactivity (25 ° C raw material temperature)
Gel time 25 seconds (5) Density 1.1 g / cm ³

Mixing head: Unipre (GSP 20)

The evaluation method is as follows.
appearance:
The presence or absence of bubbles in the cured polyurethane resin after curing for 1 day was visually observed.

Measurement of molding shrinkage (%):
The molding shrinkage (%) of the cured polyurethane resin after curing for one day with respect to the length of 500 mm of the aluminum channel was determined by the following formula.
(500-length of injected polyurethane resin (mm)) / 500 × 100

Example 1
(Aluminum channel and solid long linear set)
Prepare the above aluminum channel and in the center of its longitudinal section, (Piano wire (diameter 0.55 to 0.52 mm)) The piano wire was supported and set from both ends of the aluminum channel so that one could be placed. Both ends of the aluminum channel were sealed with tape so that the resin raw material liquid did not leak.
(Casting process for aluminum frame material)
72 g of polyurethane resin composition (about 65 cm ³ , injection time of about 3.8 seconds) mixed with a molding machine from the open top of the aluminum channel in an atmosphere of room temperature 20 ° C., the molding machine head along the aluminum channel Then, it was poured continuously while moving in parallel.
(Curing)
Then, after the polyurethane resin composition was cured, it was further cured at room temperature for 1 day.
(Evaluation)
The integrally molded polyurethane resin had a clean appearance with no air bubbles, no shrinkage, and the molding shrinkage was 0%.

Example 2
1. Solid long linear object is iron wire The operation was performed in the same manner as in Example 1 except that.
The evaluation results are shown in Table 1.

Comparative Examples 1-4
The operations were performed in the same manner as in Example 1 except that each solid long linear product shown in Table 1 was used and the injection amount was slightly adjusted according to the volume of the solid long linear product.
The evaluation results are shown in Table 1.

Comparative Example 5
As a raw material for polyurethane resin, wollastonite (average fiber length of 100 μm, average diameter of 5 to 8 μm, main component: calcium metasilicate) which is a linear filler having an aspect ratio of about 12.5 to 20 is contained in a polyol by 20% by weight. A blend (10% by weight in the resin) was prepared and operated according to Example 1 to obtain an integrally molded polyurethane resin. The evaluation results are shown in Table 1.

  The long metal material of the present invention can be used as various building parts such as window frame materials and reinforcing materials.

1 Frame material 2 Solid long linear material 3 Polyurethane resin

Claims (5)

  A metal long shape material in which a polyurethane long resin-like frame is filled with a polyurethane long resin frame, and the polyurethane resin layer is a solid long linear material having a maximum cross-sectional dimension of 0.1 to 2 mm. A long metal material encased along the direction. 2. The long metal shape according to claim 1, wherein the solid long linear material has a linear expansion coefficient of 0.5 to 30 × 10 ⁻⁶ / K and is made of metal or glass. The raw material of the polyurethane resin is
A polyether polyol having an average functionality of 2.5 to 4.0 as a polyol component;
As the isocyanate component, 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), or these Urethane modified or carbodiimide modified single or mixed,
The metal long profile according to claim 1 or 2. The long metal shape material according to any one of claims 1 to 3, wherein the solid long linear material is used in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyurethane resin. (1) A step of setting a solid long linear object having a maximum cross-sectional dimension of 0.1 to 2 mm on a metal long saddle-shaped frame;
(2) After that, a polyurethane resin-forming composition is poured into a long bowl-shaped frame at a time, and the polyurethane resin-forming composition is cured and integrally molded. A method for producing the long metal material described in 1.

Images